48th

Inorganic Discussion Weekend

48e Rencontres inorganiques

November 6-8, 2015

Royal Military College of Canada

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Itinerary

Friday, November 6th

1900-2200 Air Liquide Mixer Tir Nan Og

Saturday, November 7th

0800-0820 Registration and Coffee Baronial Hall

0820-0830 Opening Remarks Currie Hall

0830-0930 Plenary Lecture Currie Hall

0930-1000 Coffee Break Massey Hallway

1000-1120 Oral Sessions 1-2 Massey 7 and 15

1130-1230 Lunch Cadet Dining Hall

1230-1330 Poster Set-up/Exhibition New Gym

1340-1440 Oral Sessions 3-4 Massey 7 and 15

1440-1500 Coffee Break Massey Hallway

1500-1620 Oral Sessions 5-6 Massey 7 and 15

1630-1830 Poster Session New Gym

1900-2355 Banquet Yeo Hall Cadet Mess

Sunday, November 8

th

0800-0830 Coffee Massey Hallway

0830-1010 Oral Sessions 7-8 Massey 7 and 15

1010-1030 Coffee Break Massey Hallway

1030-1130 Oral Sessions 9-10 Massey 7 and 15

1145-1245 Plenary Lecture 2 Currie Hall

1245-1300 Awards and Closing Ceremonies Currie Hall

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Bus Schedule: There will be free shuttle buses between the Holiday Inn and the RMCC campus at the

following times:

Saturday between 0730-0800 and 2100-2355

Sunday between 0730-0800 and at 1300

Parking: If you are bringing your own car, there will be free parking in the Sawyer Parking Lot and you will

be issued a parking pass upon coming through the Gate House.

Poster Session: Odd-numbered posters will be judged between 1630-1730; even-numbered posters will be

judged between 1730-1830. Please be at your poster during your appointed time. There will be time to hang

your poster after lunch.

Oral Presentations: Please bring your presentation on a USB stick prior to the start of your session to be

loaded onto the Desktop. Make sure it is PC-compatible.

Exhibition: There will be several companies exhibiting at the conference. Timings to visit the booths are

after lunch between 1230-1330 and during the poster session (1630-1830). The following companies will be

present:

ACS International – CAS

Air Liquide Canada Inc.

Bruker AXS

MEGS Specialty Gases Inc.

Pine Research Instrumentation

Rigaku Oxford Diffraction

Strem Chemicals

Systems for Research

RMC Expo: After lunch, there will be several booths set-up alongside the company booths highlighting

different aspects of RMCC. Please feel free to explore the equipment and ask as many questions as you like!

If the weather is nice, you may also like to go for a walk on the RMCC campus. There will be pamphlets

available outlining the ‘War of 1812 Walking Tour’ around campus. RMCC also has several interesting

military artifacts scattered around the grounds.

Dinner Gala: Please respect the dress code and do not wear jeans.

We would like to give you a brief taste of military Mess Dinner traditions during this year’s IDW Banquet.

At the poster session, there will be a seating plan on display where you will find your name and

corresponding table. There will also be a floor plan to find the location of your table within the Cadet Mess.

Musicians will play at 15 minutes and 5 minutes before the start of dinner.

We kindly ask you to make your way into the Mess starting at 6:30pm and be standing behind your chair at

7:00pm for the arrival of the Head Table.

It is our pleasure to host you at the Royal Military College of Canada Cadet Mess. If you have any questions

or concerns, please do not hesitate to ask any member in uniform.

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Air Liquide Mixer

Time: start at 1900 (Registration ends at 2200)

Where: Tir Nan Og

200 Ontario St, Kingston, ON K7L 2Y9

(613) 544-7474

https://www.facebook.com/kingston.tirnanog

Musical Entertainment: Tangent

Drink Tickets: black tickets in your badge holder

Tir Nan Og is also open for dinner and offers great pub-style food.

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Gate House

P

Massey Building – Oral Sessions

(Rooms Massey 7 and 15)

Currie Building – Plenary Lectures

(Currie and Baronial Hall)

Yeo Hall – Lunch, Poster Session, Banquet (Cadet Dining Hall, Mess, and New Gym)

To Kingston

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Program of Events

Saturday, November 7th

, 2015

08:00-08:20 Registration and Coffee (Baronial Hall)

08:20-08:30 Opening Remarks: Dr. Gord Simons, Dean of Science, RMCC (Currie Hall)

08:30-09:30 Plenary Lecture: Dr. Ken J. Reimer, Royal Military College of Canada (Currie Hall)

09:30-10:00 Coffee Break (Massey Hallway – Sponsored by New Journal of Chemistry)

10:00-11:20 Oral Session 1 Massey 7 Massey 15

Chair: Anbareen Farooq Chair: Dr. Michelle Nearing

10:00

O1 1,2,4,6-Thiatriazinyl Radicals and Dimers:

Structural and Electronic Tuning through

Heteroaromatic Substituent Modification

O5 New Ruthenium (II) Complex with Pyrazole

Containing Ligand and its Catalytic Activity in

Transfer Hydrogenation

Nathan J. Yutronkie (University of Ottawa), A.A.

Leitch, J.A. Klein, I. Korobkov, J.L. Brusso

Iryna D. Alshakova (Brock University), G.I.

Nikonov

10:20

O2 ‘All three-in-one’: Ferromagnetic Interactions,

Single-Molecule Magnetism and Magnetocaloric

Properties in a New Family of [Cu4Ln] Clusters

O6 Synthesis and Biological Activity of Furan-

Containing Organoruthenium Complexes

Paul Richardson (Brock University), D.I.

Alexandropoulos, L. Cunha-Silva, G. Lorusso, M.

Evangelisti, J. Tang, T.C. Stamatatos

Mohammadmehdi Haghdoost (INRS-Institut), G.

Golbaghi, A. Castonguay

10:40

O3 Study of a Novel Hepta-Coordinated FeIII

Bimetalic Complex with an Unusual 1,2,4,5-

Tetrazine-Ring Opening

O7 Aqueous Biphasic Iron-Catalyzed Asymmetric

Transfer Hydrogenation of Ketones

Maykon A. Lemes (University of Ottawa), A.

Pialat, S.N. Steinmann, I. Korobkov, C. Michel, M.

Murugesu

Karl Z. Demmans (University of Toronto), O.W.K.

Ko, R.H. Morris

11:00

O4 A Mononuclear Supramolecular Capsule with

Single Molecule Magnet Behaviour

O8 Catalyst Choice in Cross-Metathesis of

Electron-Deficient Olefins: Phosphine-Induced

Catalyst Decomposition

Majeda Al Hareri (Brock University), E. Gavey,

M. Pilkington

Gwendolyn A. Bailey (University of Ottawa), D.E.

Fogg

11:30-12:30 Lunch (Cadet Dining Hall)

12:30-13:30 RMCC Exhibition and Poster Set-up (New Gym)

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13:40-14:40 Oral Session 2 Massey 7 Massey 15

Chair: Diana Tyner Chair: Laura Ogilvie

13:40

O9 Synthesis and Characterization of Side-Chain

Boron Difluoride Formazanate Polymers

O12 Towards Carrier-Mediated Water Splitting –

Catalytic Dehydrogenation of Formaldehyde

Samantha Novoa (Western University), J.A.

Paquette, S.M. Barbon, R.R. Maar, J.B. Gilroy

Nicholas Alderman (University of Ottawa), C.

Viasus, J. Sommers, V. Peneau, L. Hull, S. Alshehri,

S. Gambarotta

14:00

O10 Alkyl-Functionalization of 3,5-Bis-(2-Pyridyl)-

1,2,4,6-Thiatriazine Complexes

O13 Catalytic Hydrogenation of CO2 to Formamide

using Non-precious Metal Catalysts

Elizabeth Kleisath (University of Ottawa), N.

Yutronkie, I. Korobkov, B. Gabidullin, J. Brusso

Mohammad A. Affan (Queen’s University), P.G.

Jessop

14:20

O11 Towards Highly Conjugated and Functional

Materials: the Quest for Polyazaborinines

O14 Ruthenium and Iridium Complexes of Poly-

Pyridine Ligands as Homogeneous Catalysts for the

Hydrodeoxygenation of Biomass-Derived Substrates

to Value-Added Chemicals

Soren Mellerup (Queen’s University), S. Wang Elnaz Latifi (University of Guelph), R.J. Sullivan,

T.A. Minard, C.T. Oswin, M. Schlaf

14:40-15:00 Coffee Break (Massey Hallway – Sponsored by Systems for Research)

15:00-16:20 Oral Session 3 Massey 7 Massey 15

Chair: Summer Li Chair: Jessica Henry

15:00

O15 A Fluorescent Radical-Functionalized Poly-

Aromatic Hydrocarbon Polymer Composite

O19 Synthesis and Coordination of Amidines and

Phosphaamidines Metal Complexes

Mitchell Nascimento (University of Windsor), Y.

Beldjoudi, I. Osorio-Roman, J.M. Rawson

Ramjee Kandel (Queen’s University), K. Huynh, L.

Dalgliesh, R. Wang, P.G. Jessop

15:20

O16 Multichromic Supramolecular Dye

Architectures for Advanced Light-Harvesting

Applications

O20 Manganese(II) Dialkyl and Manganese(I) and

(III) Hydride Complexes

Muhammad Yousaf (Ryerson University), B.D.

Koivisto

Jeffrey S. Price (McMaster University), P. Chadha,

D.J.H. Emslie

15:40

O17 The Formation of Gold Thiophene Nanoreactor

By Mediating Metal-Polymer Interaction

O21 Nitrene Transfer from Organic Azides

Mediated by Metal Complexes of Bulky o-

Phenylenediamide Ligand

Vishva Shah (Royal Military College of Canada),

C. Malardier-Jugroot, M. Jugroot

Pavel Zatsepin (University of Toronto), T. Janes, D.

Song

16:00

O18 Electrochemical Characterizations of Ultra-

Stable Self-assembled Monolayers of N-

Heterocyclic Carbenes on Gold

O22 Solvent Stabilized Dinitrogen Trioxide as a

Laboratory Reagent

Zhe She (University of Toronto Scarborough), M.R.

Narouz, C.A. Smith, C.M. Crudden, J.H. Horton, H.-

B. Kraatz

Kristopher Rosadiuk (McGill University), D.S.

Bohle

16:30-18:30 Poster Session and Exhibition (New Gym) (red drink tickets in your badge holders)

19:00 Banquet (Yeo Hall)

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Sunday, November 8th

, 2015

08:00-08:30 Registration and Coffee (Baronial Hall)

08:30-10:10 Oral Session 4 Massey 7 Massey 15

Chair: Vishva Shah Chair: Matt McTaggart

08:30

O23 Evaluation of Anisole-Substituted Boron

Difluoride Formazanate Complexes for

Fluorescence Cell Imaging

O28 Iterative, Protecting Group Free Suzuki-

Miyaura Coupling of Enantioenriched

Polyboronates

Ryan R. Maar (Western University), S.M. Barbon,

N. Sharma, H. Groom, L.G. Luyt, J.B. Gilroy

C. Ziebenhaus, Jason Rygus (Queen’s University),

K. Ghozati, P.J. Unsworth, S. Voth, Y. Maekawa,

C.M. Crudden, M. Nambo

08:50

O24 Pyrido[2,1-a]-isoindole as a Novel Ligand in

Main Group and Transition Metal Chemistry

O29 Chan-Lam Coupling Using a Copper(II)

Complex with a Sulfonated Diketimine Ligand

Sean M. McDonald (Queen’s University), S. Wang Valérie Hardouin Duparc (Université de

Montréal), F. Schaper

09:10

O25 Bis-Carbene-Stabilized Phosphorus Cations O30 Stable Organopalladium(IV) Aryldiazenido

Complexes

Justin F. Binder (University of Windsor), A.

Swidan, M. Tang, J.H. Nguyen, C.L.B. Macdonald

David Armstrong (University of Toronto

Mississauga), M. Daryanavard, A.J. Lough, U.W.

Fekl

09:30

O26 Engineered Designer Monomers: The Path to

Light and Moisture Stable Polystannanes

O31 Selective C(sp2)-O Bond Formation from

Palladium Complexes by Using a Green Oxidant

Jeffrey Pau (Ryerson University), D. Foucher Ava Behnia (Western University), J.M. Blacquiere,

R.J. Puddephatt

09:50

O27 N-Heterocyclic Carbene Stabilized Ag

Nanoparticles

O32 Tuning the Steric and Electronic Properties of

Iron-Based Catalysts Using Modular Phosphine

Moieties

Iraklii I. Ebralidze (University of Toronto

Scarborough), H.-B. Kraatz

Samantha A. M. Smith (University of Toronto),

A.J. Lough, R.H. Morris

10:10-10:30 Coffee Break (Massey Hallway)

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10:30-11:30 Oral Session 5 Massey 7 Massey 15

Chair: Shuang Liang Chair: Dr. Deborah Durbin

10:30

O33 Intercalation of Coordinatively Unsaturated

FeIII

Ion within Interpenetrated MOF-5

O36 Ligand Effects in Copper-Catalyzed Aerobic

Oxygenation of Phenols

Rebecca J. Holmberg (University of Ottawa), T.

Burns, S.M. Greer, L. Kobera, S.A. Stoian, I.

Korobkov, S. Hill, D.L. Bryce, T.K. Woo, M.

Murugesu

Laura Andrea Rodríguez Solano (Concordia

University), J.-P. Lumb, X. Ottenwaelder

10:50

O34 Towards Modeling the Active Site of

Photosystem II: New Structural Motifs in Mn/Ca

Chemistry from the Use of Salicylhydroxime

O37 1,2-Diphosphonium Dication : A Strong P-

Based Lewis Acid in Frustrated Lewis Pair

Activations of B-H, Si-H, C-H and H-H Bonds

Alysha A. Alaimo (Brock University), S.J. Teat, G.

Christou, T.C. Stamatatos

Julia M. Bayne (University of Toronto), M.H.

Holthausen, I. Mallov, R. Dobrovetsky, D.W.

Stephan

11:10

O35 Single Molecule Magnets (SMM) O38 Progress in Boro-cation Catalysis for

Hydrofunctionalization

Munendra Yadav (McGill University), S. Bohle Patrick Eisenberger (Queen’s University), C.M.

Crudden

11:45-12:45 Plenary Lecture: Dr. Daniel J. Mindiola, University of Pennsylvania (Currie Hall)

12:45-13:00 Closing Ceremonies and Awards (Currie Hall)

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Plenary Speaker - Dr. Ken J. Reimer

Emeritus Professor

Department of Chemistry and Chemical Engineering, Royal Military College of Canada

Ken Reimer received his BSc (1969) and MSc (1971) degrees from the University

of Calgary; the latter dealing with tungsten and molybdenum complexes and his

PhD (1975) from the University of Western Ontario in organometallic synthesis. He

then studied bioinorganic chemistry as a Killam Postdoctoral Fellow at the

University of British Columbia. After teaching briefly at the University of Guelph,

he was appointed as an Assistant Professor at Royal Roads Military College in

Victoria, BC, reaching the rank of Professor before being transferred to the Royal

Military College of Canada in 1995. He also holds a cross-appointment to Queen’s

University School of Environmental Studies. Upon his retirement from RMCC in

2014, Dr. Reimer was appointed Emeritus Professor and he still maintains an active

research program.

Starting with a background in classical inorganic chemistry, Ken became very interested in interdisciplinary

research. This led to a focus on arsenic in the environment and included numerous sampling programs in the

coastal waters of BC to examine the effect of mine waste disposal. Environmental risk assessment was just

beginning and found application interpreting the results of these investigations that had an applied and public

component. Ken’s group expanded to include biologists and oceanographers as well as chemists and he

extended his collaboration with researchers in several other disciplines. In 1989, Dr. Reimer founded, and for

the next 25 years was Director of, the Environmental Sciences Group (ESG), a multidisciplinary team (of 60-

100 people) that conducted basic and applied environmental research all over the world. ESG was the

scientific authority for the Distant Early Warning Line cleanup – one of Canada’s largest remediation

projects. It involved some of the first environmental site assessments in Canada’s Arctic; the design of the

cleanup protocol; numerous consultations with Inuit; and oversight of the actual remediation itself. This is

just one of the hundreds of projects that typically involved remote locations, novel applications of human

health and ecological risk assessment, actual environmental cleanups and extensive interactions with

aboriginal communities. Arsenic continued to be a basic research focus but the applied work brought interest

in a diverse range of contaminants including persistent organic pollutants, chromium, lead, and cadmium.

Dr. Reimer’s creation of the ESG and its successful involvement with environmental restoration was

rewarded with two National Defence Deputy Minister Commendation Awards in 1992 and 2006. He has also

received the Chemical Institute of Canada’s Environmental Improvement Award and the RMCC Cowan

Prize for Excellence in Research. Ken has always been committed to making the results of his work

meaningful to stakeholders and, for that reason, he is particularly proud of a Real Property Institute of

Canada Award of Excellence in the Field of Contaminated Sites entitled ‘Scientists and Inuit - A Long Term

Partnership’ and a Parks Canada CEO Award of Excellence ‘for an extraordinary contribution in engaging

partnerships with the Inuvialuit. Ken is a Past Chair of the Environment Division of the Chemical Institute of

Canada and is the current Chair of BioAcessibility Research Canada.

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Plenary Speaker - Dr. Daniel J. Mindiola

Presidential Professor

Department of Chemistry, University of Pennsylvania

Daniel José Mindiola was born in San Cristóbal, Venezuela in 1974. Upon entering

the US with his mother in 1989, Daniel then pursued the remainder of high school in

a small town in mid-Michigan (Ovid). Daniel began his college education at

Michigan State University, East Lansing, MI, in 1992. As a "Spartan", he spent the

next three and a half years learning the principles of inorganic chemistry under the

auspices of Professor Kim R. Dunbar. After obtaining his B.S. degree in chemistry

from MSU in 1996, Daniel then attended the Massachusetts Institute of Technology

in Cambridge, MA, under the guidance of Professor Christopher "Kit" Cummins. In

the summer of 2000, Daniel completed his PhD. degree and continued work in small

molecule chemistry as an NIH and FORD post-doctoral fellow in the laboratories of

Professor Gregory L. Hillhouse at the University of Chicago.

After nearly two years at Chicago, Daniel accepted an invitation to join the Chemistry Faculty at Indiana

University in the city of Bloomington, IN (July of 2002). In 2007, he was promoted to Associate Professor

with tenure, and in 2011 to Full Professor. He was the departmental Graduate Advisor from 2008-09 and

Chair of Graduate Admissions at IU-Chemistry from 2010-2013. His research work entails the design and

assembly of reactive metal complexes of early metals (in particular 3d metals) and their role in unusual

transformations such as C-H activation and C-N bond cleavage reactions. He is also interested in novel

catalytic processes mediated by reactive complexes containing metal-ligand multiple bonds.

In the summer of 2013 and after 11 wonderful years in Bloomington, Daniel moved to the University of

Pennsylvania where he holds a Presidential Chair Professorship. In 2014, Daniel was elected as a Fellow of

the Royal Society of Chemistry (FRSC) and is Associate Editor for the ACS journal Organometallics. He

formally was an Associate Editor for Dalton Transactions for 3 years. He has given over 140 lectures

worldwide and published over 140 papers in peer-reviewed journals. Other accolades prior to 2013 include:

Fellow, Japan Society for the Promotion of Science; Fellow, Chemistry Research Promotion Center, National

Science Council of Taiwan; College of Natural Science Recent Alumni Award (Michigan State University);

American Chemical Society National Fresenius Award (Phi Lambda Upsilon); Friedrich Wilhelm Bessel

Research Award (Humboldt Foundation); Dalton Lecture Award; University of California at Berkeley;

Camille and Henry Dreyfus New Faculty Award; NSF Presidential Early Career Award for Scientists and

Engineers (PECASE); Alfred P. Sloan Research Fellow; Camille Dreyfus Teacher-Scholar Award; and NSF

CAREER Award.

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Plenary Lecture 1 – Saturday, November 7th

, at 08:30 in Currie Hall

Arsenic in the environment, in consumer products, and in you.

Are you at risk?

Ken J. Reimer

Environmental Sciences Group, Department of Chemistry and Chemical Engineering, Royal

Military College of Canada

Email: reimer-k@rmc.ca

Recent media articles shock readers with statements like: ‘Arsenic in rice and baby foods’, ‘Arsenic in Red

Wine’, and ‘Arsenic in Apple Juice’ (with the quote: ‘I didn’t know that I was giving poison to my child’).

These attract attention because most people feel that arsenic is synonymous with poison. Arsenic (as arsenic

trioxide) is poisonous and in the Middle Ages was readily available from smelting of gold ore. It was also

colourless, odourless, and tasteless and became so popular that it was known as the ‘King of Poisons’.

Popular writers like Agatha Christie and plays like ‘Arsenic and Old Lace’ further popularized the notion that

arsenic had to be bad.

The real situation is somewhat more complex. For example, when I am asked to comment on those

newspaper headlines I respond with a statement that is counterintuitive to many people. I say ‘of course we

should find arsenic in rice; arsenic is everywhere and it would be more surprising if we did not find it in our

food and drink.’

This talk will describe the ubiquitous presence of arsenic in our environment. Arsenic is present in over 300

minerals and natural weathering processes, together with biogeochemical transformations, redistribute

arsenic into approximately 50 different chemical forms. We know how most of these transformations take

place, including how humans metabolize arsenic, but the production of the one non-toxic arsenical –

arsenobetaine, continues to elude us. We also know that high doses of inorganic arsenic will cause numerous

health effects, including cancer, but there is an intense debate about possible health effects caused by the low

dose that we all experience each day. Low dose may be the norm, but there are situations (such as old mine

sites) where arsenic has been redistributed in the environment in very large amounts. Case studies will be

used to examine how chemists can assist in dealing with such problems and with public concerns regarding

arsenophobia.

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Plenary Lecture 2 – Sunday, November 8th

, at 11:45 in Currie Hall

New Developments in Dehydrogenation of Volatile Alkanes with Ti-C Multiple

Bonds.

Daniel J. Mindiola

Department of Chemistry, University of Pennsylvania, Philadelphia, PA

E-mail: mindiola@sas.upenn.edu

We will present the reactivity of a transient titanium alkylidyne (PNP)Ti≡CtBu (PNP = N[2-P(CHMe2)2-4-

methylphenyl]2–), specifically how this species engages in intermolecular C-H activation and

functionalization reactions. Such species can dehydrogenate methane, and C2-C8 alkanes selectively at the

terminal position (in the case of linear alkane C4-C8) to form the olefin product. The mechanism to this

transformation as well as other new reactions such as the dehydrogenation of cyclohexane and trapping

reactions will be presented and discussed. A new catalytic cycle for dehydrogenation of alkanes will be also

discussed as well as the formation of new Ti-C mulitiply-bonded scaffolds such as phosphino-alkylidenes

and alkylidynes and phosphonio-alkylidynes.

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O1 1,2,4,6-Thiatriazinyl Radicals and Dimers: Structural and Electronic Tuning

through Heteroaromatic Substituent Modification

Nathan J. Yutronkie, Alicea A. Leitch, Jacob A. Klein, Ilia Korobkov, and Jaclyn L. Brusso*

Centre for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, Ottawa, ON, Canada nyutr055@uottawa.ca; jbrusso@uottawa,ca

For some time, thiazyl-based neutral radicals have been recognized as attractive candidates for molecular conductors

and magnets, in addition to implementation as spin-bearing ligands or liquid

crystalline radicals. The 1,2,4,6-thiatriazinyl (TTA) radical is an ideal system in

regards to the aforementioned applications as variation in the R substituent can

be used to alter the molecular and solid state properties. To this end, a series of

TTA radicals have been prepared and investigated with substituted

heteroaromatic susbstituents (e.g. thienyl, pyridyl, pyrimidyl). The 3,5-bis(2-

pyridyl)-1,2,4,6-thiatriazinyl (Py2TTA) and 3,5-bis(2-pyrimidyl)-1,2,4,6-

thiatriazinyl (Pm2TTA) radicals can been viewed as attractive candidates

towards spin-bearing ligands with binding motifs sturcturally similar to

terpyridine. Additionally, the 3,5-bis-(2-thienyl)-1,2,4,6-thiatriazinyl radical (Th2TTA) has been targeted as building

blocks in multifuctional materials as facile functionalization on the thienyl substutuents can give rise to the potential of

discotic liquid crystalline materials. This presentation will focus on the development of these radicals in regards to their

synthesis, characterization, and crystal structures.

O2 ‘All Three-in-One’: Ferromagnetic Interactions, Single-Molecule Magnetism and

Magnetocaloric Properties in a New Family of [Cu4Ln] Clusters

Paul Richardson,1 Dimitris I. Alexandropoulos,

1 Luís Cunha-Silva,

3 Giulia Lorusso,

4 Marco Evangelisti,

4 Jinkui

Tang,2 and Theocharis C. Stamatatos

*,1

1Department of Chemistry, Brock University, St. Catharines, ON, Canada;

2State Key Laboratory of Rare

Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, P. R. China;

3REQUIMTE / LAQV & Department of Chemistry and Biochemistry, Faculty of

Sciences, University of Porto, Porto, Portugal; 4Instituto de Ciencia de Materiales de Aragón (ICMA) and

Departamento de Física de la Materia Condensada, CSIC-Universidad de Zaragoza, Zaragoza, Spain pr07xq@brocku.ca; tstamatatos@brocku.ca

Modern coordination chemistry, as a field of scientific research, has expanded greatly over the past decades, finding

interests in not only isolating aesthetically pleasing structures, but also probing the magnetic properties of these

compounds, such as single-molecule magnetism (SMM) or the magnetocaloric effect (MCE). These two phenomena

share common characteristics; both are enhanced by a high-spin ground state,

which mainly arises from ferromagnetic interactions between the metal ions

present. The desire for high-spin molecules, which is aided by a large number of

unpaired electrons in the metal ion(s), lead to the employment of lanthanide (Ln)

ions, either in homometallic 4f- or heterometallic 3d/4f-chemistry. To form such

high-spin molecules, the use of different ligands must be investigated; both

bridging and chelating ligands are necessary to increase the nuclearity and

thermodynamic stability of the compound and simultaneously prevent the

extensive polymerization of the metal ions. Through the use of the bridging and

chelating ligand naphthalene-2,3-diol (ndH2), a new [Cu4Ln] family of clusters

was isolated and characterized (Figure). This family was studied in detail with

respect to their magnetic properties, searching for SMM behaviour in both the

TbIII

and DyIII

analogues, as well as MCE in the GdIII

analogue.1

1. P. Richardson, D. I. Alexandropoulos, L. Cunha-Silva, G. Lorusso, M.

Evangelisti, J. Tang, Th. C. Stamatatos, Inorg. Chem. Front. 2015, 2, 945.

Figure. Structure of [Cu4Gd(nd)8]5-

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O3 Study of a Novel Hepta-coordinated Fe

III Bimetalic Complex with an Unusual

1,2,4,5-Tetrazine-Ring Opening

Maykon A. Lemes,a Amélie Pialat,

a Stephan N. Steinmann,

b Ilia Korobkov,

a Carine Michel,

b and Muralee

Murugesua,*

aDepartment of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, ON, Canada;

bLaboratoire de Chimie UMR5182, Université de Lyon, CNRS, Ecole Normale Supérieure de Lyon, Lyon

cedex 07, France mleme031@uottawa.ca; m.murugesu@uottawa.ca

Reaction of Fe(NO3)3 with 3,6-di(pyrimidin-2-yl)-1,2,4,5-tetrazine (BPymTz) in acetonitrile gives a hepta-coordinated

FeIII

complex (1) with the bridging unit 1,2-diiminohydrazido (1,2-dih2-

: —

HN—C(R)=N—N=C(R)—NH—

) generated

in-situ from the tetrazine ring-opening of BPymTz. DFT calculations, X-ray diffraction studies and SQUID

magnetometry measurements, have been performed on 1. The crystallography measurement confirms the ring-opening

and the substituent’s contribution to the rare pentagonal bipyramidal coordination geometry of the metal ions. Magnetic

susceptibility measurements performed on 1 reveal an S = 0 ground state, arising from a weak antiferromagnetic

interaction between the two FeIII

centres (J = -3.025 cm-1

).

O4 A Mononuclear Supramolecular Capsule with Single Molecule Magnet Behaviour

Majeda Al Hareri, Emma Gavey, and Melanie Pilkington*

Department of Chemistry, Brock University, St. Catharines, ON, Canada ma10hk@brocku.ca; mpilkington@brocku.ca

Many lanthanide ions display great potential in the field of molecular magnetism due

to their high intrinsic anisotropies1, which can be enhanced by an appropriate

coordination environment. However, many of the ligand systems employed to date

require multi-step syntheses and result in complexes which are unstable to air or

moisture.1,2

Our approach has been to make use of the inherently oxophilic nature of

lanthanide ions and employ oxygen-rich ligands, such as the tuneable crown ethers.

Our group has recently reported the synthesis of a novel family of half-sandwich and

sandwich-like complexes that exhibit single molecule magnet (SMM) behaviour.3 A

new addition to this family, a mononuclear DyIII

capsule (1) comprising of three H-

bonded benzo-15-crown-5 ligands, also exhibits the slow relaxation of magnetization

consistent with SMM properties. This family collectively represents the first example

of the exploitation of crown ethers as ligands for the formation of mononuclear lanthanide SMMs.

1 D. N. Woodruff, R.E.P. Winpenny, R.A. Layfield, Chemical Reviews, 2013, 113, 7, 5110-5148.;

2 F. Chibotaru, M.

Murugesu et al., Journal of the American Chemical Society, 2013, 135, 3502-3510.; 3 M. Pilkington et al., J. Mater.

Chem. C, 2015, 3, 7738.

18

O5 New Ruthenium (II) Complex with Pyrazole Containing Ligand and its Catalytic

Activity in Transfer Hydrogenation

Iryna D. Alshakova and Georgii I. Nikonov*

Department of Chemistry, Brock University, St. Catharines, ON, Canada iryna.alshakova@brocku.ca; gnikonov@brocku.ca

Ruthenium occupies a prominent position in catalytic hydrogenation and transfer hydrogenation (TH) of unsaturated

substrates. Several families of bifunctional Ru-based catalysts have been developed. Recently, heterocycle-based

ligands have received significant attention, and in particular pyrazole-supported Ru complexes were found to be

effective in the catalytic TH.[1]

Given these literature precedents and our previous research on phosphine supported

catalytic TH of challenging substrates, we designed of a new bifunctional pyrazole-phosphine ligand (N,P). Screening of

potential Ru catalysts resulted in the preparation of complex 1 which happened to be a highly active catalyst for the TH

of nitriles, olefins, and heteroaromatics.

[1] a) S. F. L. T. Ghoochany, Y. Sun, and W.R. Thiel, Eur. J Inorg. Chem. 2011, 3431-3437; b) P. W. W. Du, Q.

Wang, and Z. Yu, Organometallics 2013, 32, 3083-3090.

O6 Synthesis and Biological Activity of Furan-Containing Organoruthenium

Complexes

Mohammadmehdi Haghdoost, Golara Golbaghi, and Annie Castonguay*

INRS-Institut Armand-Frappier, Laval, QC, Canada Mehdi.Haghdoost@iaf.inrs.ca; Annie.Castonguay@iaf.inrs.ca

Transition metal complexes have unique properties, notably due to their partially filled d-orbitals, and can offer great

opportunities to the field of chemotherapy, leading to the discovery of new modes of action for therapeutics and novel

interactions with biomolecules. Of particular interest, ruthenium complexes display great advantages over platinum-

based drugs that are commonly used for cancer therapy. Our research aims at the discovery of novel multitasking

anticancer drug candidates, by combining ruthenium complexes and biologically active organic molecules.

Numerous furan-containing compounds were reported to display anticancer, as well as anti-inflammatory and

antimicrobial activities. As an added value, the presence of a furan ring in the backbone of inorganic complexes offers

the unique possibility to link them to cancer cell targeting agents or drug delivery systems via furan-maleimide Diels-

Alder cycloadditions. This type of linkage can then undergo thermal disassembly at physiological temperature, and

allow the release of furan-containing therapeutics.

The focus of this presentation will be on the synthesis and characterization of Ru(II)-arene complexes with pendant

furan arms, and our preliminary results regarding their in vitro anticancer activity against human breast cancer cells.

1

19

O7 Aqueous Biphasic Iron-Catalyzed Asymmetric Transfer Hydrogenation of Ketones

Karl Z. Demmans, Oliver W. K. Ko,* and Robert H. Morris

*

Department of Chemistry, University of Toronto, Toronto, ON, Canada kdemmans@chem.utoronto.ca; oliver.ko@mail.utoronto.ca; robert.morris@utoronto.ca

For the first time, an iron (II) catalyst is used in the biphasic asymmetric transfer hydrogenation (ATH) of ketones to

enantioenriched alcohols employing water and potassium formate as the proton and hydride source. The precatalyst

[FeCl(CO)(P-NH-N-P)][BF4] (P-NH-N-P = (S,S)-PPh2CH2CH2NHCHPhCHPhNCHCH2PPh2) in the organic phase with

the substrate is activated by base to produce a system that rivals the best ruthenium biphasic ATH catalysts in activity

but not enantioselectivity. Biorenewable 2-methyltetrahydrofuran was added as a cosolvent to greatly enhance the

catalyst’s activity. The enantioselectivity of the reduction ranged from 3 to 88% depending on the substitution pattern of

the arylketone employed. NMR studies verify the formation of an iron hydride

[FeH(CO)(PPh2CH2CH2NHCHPhCHPhNCHCHPPh2] intermediate as was observed in our 2-propanol-based ATH

studies.

O8 Catalyst Choice in Cross-Metathesis of Electron-Deficient Olefins: Phosphine-

Induced Catalyst Decomposition

Gwendolyn A. Bailey and Deryn E. Fogg*

Centre for Catalysis Research and Innovation, University of Ottawa, Ottawa, ON, Canada gbail025@uottawa.ca; dfogg@uottawa.ca

In the past two years, olefin metathesis has seen its long-

awaited implementation in pharmaceutical and specialty-

chemicals manufacturing.1,2

Fundamental questions relating to

catalyst deactivation pathways hence take on intensified

importance. We recently described the incompatibility of the

dominant Grubbs catalyst GII (Chart 1) with acrylates. The

PCy3 ligand used to stabilize the precatalyst reacts with these

electron-deficient olefins to generate strongly basic enolate A,

which then triggers catalyst decomposition by abstracting a proton from the metallacyclobutane intermediate.3 The

scope of this behaviour is of keen interest from the emerging perspective of metathesis of directly-functionalized

olefins. Here we explore its dependence on the electronic nature of the olefin substituent, and on the basicity of the

phosphine ligand.

[1] (a) Nickel, A.; Pederson, P. L. in Olefin Metathesis – Theory and Practice (Ed.: K. Grela), Wiley, Hoboken, 2014,

pp. 335–348. (b) Fandrick, K. R.; Savoie, J.; Yee, N; Song, J. J.; Senanayake, C. H. in Olefin Metathesis – Theory and

Practice (Ed.: K. Grela), Wiley, Hoboken, 2014, pp. 349–366.

[2] Higman, C. S.; Lummiss, J. A. M.; Fogg, D. E. Angew. Chem. Int. Ed. 2016, accepted.

[3] Bailey, G. A.; Fogg, D. E. J. Am. Chem. Soc. 2015, 137, 7318–7321.

20

O9 Synthesis and Characterization of Side-Chain Boron Difluoride Formazanate

Polymers

Samantha Novoa, Joseph A. Paquette, Stephanie M. Barbon, Ryan R. Maar, and Joe B. Gilroy*

Department of Chemistry, Western University, London, ON, Canada snovoa@uwo.ca; joe.gilroy@uwo.ca

Boron difluoride (BF2) complexes of formazanate ligands (e.g., 1) are

a class of molecular materials that offer structurally tunable

spectroscopic properties, moderate to high fluorescence quantum

yields and redox activity.1 Due to their promising properties, we set

out to incorporate triaryl formazanate BF2 complex 1 into polymers 2

through ring-opening metathesis polymerization (ROMP) of a pendant

norbornene group using Grubbs' 3rd generation catalyst (GIII).2

Mechanistic studies revealed the controlled nature of this

polymerization. Moreover, the unique properties of the BF2 complex

were retained upon polymerization. The polymers are strongly

absorbing in the visible region, are fluorescent, exhibit large Stoke's

shifts, and can be reversibly reduced to borataverdazyl-based poly(radical anions) electrochemically. Recent progress in

this area will be presented.

1. S. M. Barbon, P. A. Reinkeluers, J. T. Price, V. N. Staroverov and J. B. Gilroy, Chem. Eur. J., 2014, 20,

1134011344.

2. S. Novoa, J. A. Paquette, S. M. Barbon, R. R. Maar, J.B. Gilroy, 2015, Submitted.

O10 Alkyl-functionalization of 3,5-bis-(2-pyridyl)-1,2,4,6-thiatriazine Complexes

Elizabeth Kleisath, Nathan Yutronkie, Ilia Korobkov, Bulat Gabidullin, and Jaclyn Brusso*

Department of Chemistry, University of Ottawa, Ottawa, ON, Canada eklei031@uottawa.ca; jbrusso@uottawa.ca

A novel synthesis of alkyl-functionalized 3,5-bis(2-pyridyl)-4-hydro-1,2,4,6-thiatriazine (Py2TTAH) complexes through

post thiatriazine (TTA) ring formation will be presented. This marks the first reported example of S-alkylation in TTA

complexes starting from a stable synthetic precursor. Either discrete cations or coordination polymer structures are

obtained, depending on the electrophilicity of the

alkylating agent used. In addition, the relative

susceptibility of the Py2TTAH heteroatoms

towards alkylation was determined; initial

alkylation occurred at the sulfur of the TTA ring,

and then additionally on the nitrogen atoms of

the pyridine substituents. Single crystal X-ray

analysis highlights the differences in chemical

environment and crystallographic packing

between the discrete molecules in comparison to

the 1D coordination polymer. The versatile

heteroatom-alkylation synthesis for TTAs will be

presented, along with characterization studies of

the resulting compounds.

21

O11 Towards Highly Conjugated and Functional Materials: the Quest for

Polyazaborinines

Soren Mellerup and Suning Wang*

Department of Chemistry, Queen’s University, Kingston, ON, Canada soren.mellerup@chem.queensu.ca; suning.wang@chem.queensu.ca

Recently, our research group observed that BN-heterocycles (B; Figure 1) display unique reactivity when exposed to

different stimuli such as heat or light, ultimately generating either pyrido[1,2-a]isoindole (A) or BN-phenanthrenes (C)

respectively.1 Due to the simplicity and selectivity of each transformation, we set out to design new precursors

consisting of multiple BN-heterocyclic components such that the application of either heat or light would induce the

formation of highly -conjugated materials

containing several pyrido[1,2-a]isoindole or

BN-phenanthrene functionalities. This

presentation will focus on the synthesis of

these interesting molecules, their

photo/thermal reactivities, and evaluation of

the highly conjugated products.

Figure 1. The varying reactivity of BN-heterocyles B.

1) Yang, D.T.; Mellerup, S.K.; Wang, X.; Lu, J.S.; Wang, S. Angew. Chem. Int. Ed. 2015, Accepted.

O12 Towards Carrier-Mediated Water Splitting – Catalytic Dehydrogenation of

Formaldehyde

Nicholas Alderman, Camilo Viasus, Jacob Sommers, Virginie Peneau, Laura Hull, Salimah Alshehri, and Sandro

Gambarotta*

Department of Chemistry, University of Ottawa, Ottawa, ON, Canada

nickalderman@gmail.com; sgambaro@uottawa.ca

A major problem with current photochemical water splitting systems such as TiO2 is the inhibitive cost of gas (O2/H2)

separation, which can add hundreds of million dollars to plant designs. Therefore a system which can release carbon and

hydrogen in two different environments would negate the need for expensive gas separation. We propose a catalytic

cycle based upon the oxidation and reduction of a carbon carrier, expelling hydrogen in one step and re-hydrogenation

(using water and releasing oxygen) in another step. We have been investigating the use of the formaldehyde-formate

couple, and show promising preliminary results in an overall water splitting cycle using this technique.

22

O13 Catalytic Hydrogenation of CO2 to Formamide using Non-precious Metal Catalysts

Mohammad A. Affan and Philip G. Jessop*

Department of Chemistry, Queen’s University, Kingston, ON, Canada 12maa7@queensu.ca; jessop@queensu.ca

Catalytic hydrogenation of CO2 is an efficient and selective way to form value added fine chemicals such as formic acid

derivatives, but most of the highly active catalysts have required precious metals. Eighteen non-precious metal

precursors have been screened with six types of phosphine/hemilabile ligands for the catalytic hydrogenation of CO2

with morpholine to formamide. Twelve non-precious metal precursors have also been screened with two diphosphine

ligands for the catalytic hydrogenation of CO2 with 2-ethylhexylamine to formamide. The most active catalysts for the

hydrogenation of CO2 for the formylation of morpholine or 2-ethylhexylamine are [MX2(dmpe)2] (M = Fe(II) and

Ni(II); X = Cl-, CH3CO2-; acac

-; dmpe = 1,2-bis(dimethylphosphino)ethane) in DMSO. Morpholine and 2-

ethylhexylamine are formylated at 100 o

C and 135 oC, respectively, at a total pressure of 100 bar. Morpholine was

formylated with a TON up to 18,000, which is approaching the range of TON values reported for noble metal-phosphine

complexes. 2-Ethylhexylformamide was obtained with a TON up to 1,600. With the appropriate selection of catalyst

and reaction conditions, >90-98% conversion of amine was achieved to form a formamide.

O14 Ruthenium and Iridium Complexes of Poly-pyridine Ligands as Homogeneous

Catalysts for the Hydrodeoxygenation of Biomass-derived Substrates to Value-

added Chemicals

Elnaz Latifi, Ryan J. Sullivan, Thomas A. Minard, Christopher T. Oswin, and Marcel Schlaf*

Department of Chemistry, University of Guelph, Guelph, ON, Canada elatifi@uoguelph.ca; mschlaf@uoguelph.ca

The series of the water-soluble tri/tetradentate amino-poly-pyridine ligand based homogeneous Ruthenium/Iridium

catalysts (1-5) was evaluated for the conversion of biomass derived 2,5-hexanedione and 2,5-dimethylfuran to the

hydrodeoxygenated value-added products 2,5-hexanediol, 2,5-dimethyltetrahydrofuran and hexane in aqueous acidic

medium at high temperatures (150−225 °C) under hydrogen gas (5.5 MPa). The systems are active but limited by

thermal decomposition. Catalyst (1) decomposes at T ≥ 225 °C to the inactive bis-chelate complex [(4′-Ph-terpy)2Ru]2+

and an inactive metallic ruthenium coating. 2 decomposes at T > 175 °C acting as a heterogeneous Ir0 catalyst. 3

decomposes at T ≥ 175 °C by formation of marginally active Ru0. 4 also shows good activity for the conversion of 2,5-

hexanedione to 2,5-hexanediol and 2,5-dimethyltetrahydrofuran at 175 and 200 °C with decomposition observed only at

T ≥ 225 °C. 5 is capable of converting 5-hydroxy-methylfurfural-acetone aldol adducts to the highly valuable 2,5,8-

nonatriol in moderate yields, but deactivation via formation of the bis-chelate was again observed at T ≥ 200 °C.

23

O15 A Fluorescent Radical-Functionalized Poly-Aromatic Hydrocarbon Polymer

Composite

Mitchell Nascimento, Yassine Beldjoudi, Igor Osorio-Roman, and Jeremy M. Rawson*

Department of Chemistry and Biochemistry, University of Windsor, Windsor, ON, Canada nascime@uwindsor.ca; jmrawson@uwindsor.ca

Radicals have recently been proposed as excellent candidates for light-emitting devices such as OLEDs due to their

theoretical 100% efficient doublet excitation/relaxation process1. Here we describe a phenanthrene-functionalised

dithiadiazolyl radical (1). The radical is a diamagnetic dimer in the solid state but dissociates to form monomers in

solution. Spectroscopic studies reveal excitation at 254 nm affords a bright blue

emission at 410 nm. TD-DFT studies indicate that the initial absorption giving rise to

the fluorescence is not radical based and the non-participation of the radical electron in

the fluorescence process is evidenced by the observation that the salt [1][GaCl4]

exhibits a similar broad emission at 410 nm. Incorporation of 1 into PMMA and PS

polymer matrices afford smooth homogeneous blue emissive polymer films whose

lifetimes are 10 to 100 times greater than 1 in solution.

1. Q. Peng, A. Obolda, M. Zhang and F. Li, Angew. Chem. Int. Ed., 2015, 54, 7091.

O16 Multichromic Supramolecular Dye Architectures for Advanced Light-Harvesting

Applications

Muhammad Yousaf and Bryan D. Koivisto*

Department of Chemistry and Biology, Ryerson University, Toronto, ON, Canada myousaf@ryerson.ca; bryan.koivisto@ryerson.ca

Shape-persistent phenylacetylene macrocycles have been explored in a number of optoelectronic and light-harvesting

applications, including two-photon absorption. Likewise, BODIPY

(4,4-difluoro-4-bora-3a,4a-diaza-s-indacenes) dyes have also been

extensively used in material applications, owing to their tunable,

intense absorption and sharp emission peaks exhibiting high quantum

yields. Employing the BODIPY molecule orthogonal to the

phenylacetylene-macrocycle results in energy transfer from macrocycle

to the BODIPY core. The novel dye design could potentially be used in

the dye-sensitized solar cells (DSSCs). The DSSC is a next-generation

photovoltaic device that incorporates a dye molecule as a light-

absorber. The dyes for the DSSC are generally comprised of a redox-

active donor/chromophore (D) that is coupled through a conjugated

linker (π) to an acceptor (A) capable of anchoring to TiO2 (i.e. D-π-A

motif). The BODIPY-macrocycle dye motif can be used as a π-spacer

in the DSSC dye (as shown in Fig.) and could permit two-photon

absorption resulting in panchromatic absorption.

24

O17 The Formation of Gold Thiophene Nanoreactor by Mediating Metal-Polymer

Interaction

Vishva Shah,1 Cecile Malardier-Jugroot,

1,* and Manish Jugroot

2

1Department of Chemistry and Chemical Engineering;

2Department of Mechanical and Aerospace

Engineering, Royal Military College of Canada, Kingston, ON, Canada vishva.shah@rmc.ca; cecile.malardier-jugroot@rmc.ca; manish.jugroot@rmc.ca

Gold nanoparticles have many applications in a variety of fields ranging from clinical chemistry to targeted drug

delivery. The size and the shape of the nanoparticles have proven to be important factors in determining the physical and

electronic properties of the nanoparticles, it is therefore important to use a template for the synthesis of highly ordered

gold nanoparticles. Poly(styrene-alt-maleic acid), SMA, is an amphiphilic alternating co-polymer which self assembles

in water into highly organized nanostructures and is a good candidate for use as a template. Indeed, this template has

been used successfully for an environmentally friendly synthesis of organic polymers (polypyrrole) as well as metal

nanoparticles(gold and platinum). Pyrrole was found to spontaneously polymerize within the confined hydrophobic

cavity of SMA whereas gold was found to form an atomically-thin gold monolayer on the outer hydrophilic surface of

SMA. In this study, we combined both of these results to control the interaction between SMA and gold in three ways

including sonication, altering the nature of the polymer and by using thiophene, a structurally similar molecule to

pyrrole, to exploit the well-known gold-sulphur bond to draw the gold(I) chloride precursor into the confined regions of

SMA. Since thiophene makes a strong bond with gold, we also studied the effect of this interaction on the interaction

between gold and SMA, which could make the hydrophobicity or hydrophillicity of the metal salt irrelevant. Moreover,

it was previously observed that the confined cavities of SMA also forced the direct reduction of hydrophobic metal salts

into platinum nanoclusters. The role and the effect of the interaction between the hydrophilic or hydrophobic cavities of

the template and the metal salt on the shape and size of the gold nanoparticles will be emphasized. The ability to

mediate the metal-polymer interaction by a coupling agent opens up many more possibilities for applications in

medicine, industry, and academia.

O18 Electrochemical Characterizations of Ultra-stable Self-assembled Monolayers of N-

heterocyclic Carbenes on Gold

Zhe She,1,2

Mina R. Narouz,3 Christene A. Smith,

3 Cathleen M. Crudden,

3,4 J. Hugh Horton,

3 and Heinz-Bernhard

Kraatz1,5,*

1Department of Physical and Environmental Sciences, University of Toronto Scarborough, Toronto, ON,

Canada; 2Department of Chemistry and Chemical Engineering, Royal Military College of Canada,

Kingston, ON, Canada; 3Department of Chemistry, Queen's University, Kingston, ON, Canada;

4Institute

of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Chikusa, Nagoya, Japan; 5Department

of Chemistry, University of Toronto, Toronto, ON, Canada

zhe.she@utoronto.ca; bernie.kraatz@utoronto.ca

A self-assembled monolayer (SAMs) is a layer of organic molecules assembled at surfaces often stabilized by high

binding affinities between the molecules and the surface substrate and by van der Waals interactions between adjacent

molecules. Film formed by the interaction of S-containing molecules and Au surfaces giving rise to strong Au-S

bonding has dominated this area of research since the first reports of Au-thiolate films by Nuzzo and Whitesides et al.

(1). Recently, N-heterocyclic carbenes based SAMs were reported to be more stable than traditional Au-S SAMs (2).

Here, we report the electrochemically characterization of these films, and provide information of their stability,

molecular density and electron transfer properties of carbene films.

(1) Bain, C. D.; Troughton, E. B.; Tao, Y. T.; Evall, J.; Whitesides, G. M.; Nuzzo, R. G. J. Am. Chem. Soc. 1989, 111,

321.

(2) Crudden, C. M.; Horton, J. H.; Ebralidze, I. I.; Zenkina, O. V.; McLean, A. B.; Drevniok, B.; She, Z.; Kraatz, H.-B.;

Mosey, N. J.; Seki, T.; Keske, E. C.; Leake, J. D.; Rousina-Webb, A.; Wu, G. Nature Chemistry 2014, 6, 409.

25

O19 Synthesis and Coordination of Amidines and Phosphaamidines Metal Complexes

Ramjee Kandel, Keith Huynh, Lauren Dalgliesh, Ruiyao Wang, and Philip G. Jessop*

Department of Chemistry, Queen’s University, Kingston, ON, Canada

kandel.ramjee@queensu.ca; jessop@queensu.ca

Transition metal complexes incorporating amidines and phosphaamidines ligands, have received less attention

and coordination chemistry is less known. They could interesting for their coordination chemistry and possibly of

catalysis.

Amidines are nitrogen containing bases where the unsaturated nitrogen is more active towards coordination and

can be easily protonated. Research in our laboratory has exploited the basicity of amidines as promoters of CO2 fixation

to other products, while phosphaamidines are hybrid ligands containing a basic hard donor nitrogen atom and a soft

donor phosphorus atom. The design of acyclic phosphaamidine is attractive as the tunable Nimine should retain its

basicity while the P should preferentially coordinate to the most transition metals.

In this light, we have prepared a series of tunable acyclic amidines and phosphaamidines and tested their

coordinating abilities with Cu(I) and other transition metal ions. Amidines coordinated through only Nimine leaving Namine

free while phosphaamidines coordinate through phosphorus and Nimine depending upon the electronic and steric

properties of the phosphaamidines.

O20 Manganese(II) Dialkyl and Manganese(I) and (III) Hydride Complexes

Jeffrey S. Price, Preeti Chadha, and David J. H. Emslie*

Department of Chemistry and Chemical Biology, McMaster University, Hamilton, ON, Canada pricej4@mcmaster.ca; emslied@mcmaster.ca

With a view towards the development of new organometallic precursors and reactivities for manganese metal atomic

layer deposition (ALD), the solid state structures and properties of [{Mn(μ-R)2}∞] (1; R = CH2SiMe3), [{Mn(R')(μ-

R')2}2{Mn(μ-R')2Mn}] (2; R' = CH2CMe3), [Mn(R)2(dmpe)] (3; dmpe = 1,2-bis(dimethylphoshino)ethane), [{Mn(R')2(μ-

dmpe)}2] (4), [{Mn(R)(μ-R)}2(μ-dmpe)] (5), [{Mn(R')(μ-R')}2(μ-dmpe)] (6), [{Mn(R)(μ-R)}2(μ-dmpm)] (7; dmpm =

bis(dimethylphoshino)methane), and [{Mn(R')(μ-R')}2(μ-dmpm)] (8) are reported. Syntheses for 1-4 have previously

been published, but the solid state structures and most properties of 2-4 had not been described. Compounds 5 and 6,

with a 1:2 dmpe:Mn ratio, were prepared by reaction of 3 and 4 with base-free 1 and 2, respectively. Compounds 7 and

8 were accessed by reaction of 1 and 2 with 0.5 or more equivalents of dmpm per manganese. An X-ray structure of 2

revealed a tetrametallic structure with two terminal and six bridging alkyl groups. The solid state structures of

bisphosphine-coordinated 3-8 revealed three distinct structure types: (a) monometallic [LMnX2], (b) dimetallic

[X2Mn(µ-L)2MnX2], and (c) dimetallic [{XMn(µ-X)}2(µ-L)] (X = R or R'; L = dmpe or dmpm). Reactions of 1-8 with

H2 (25-120 °C) afforded manganese metal. By contrast, reaction of 1-8 with ZnEt2 (25 °C) afforded a ~ 1:1 Mn:Zn

alloy, accompanied in the case of dmpe-containing 3-6 by the formation of [Mn(dmpe)2(ethylene)(H)] (9). The solid

state structure of 9 is reported, along with oxidative addition reactivity leading to new manganese(III) hydride

complexes.

26

O21 Nitrene Transfer from Organic Azides Mediated by Metal Complexes of Bulky o-

Phenylenediamide Ligand

Pavel Zatsepin, Trevor Janes, and Datong Song*

Department of Chemistry, University of Toronto, Toronto, ON, Canada

pavel.zatsepin@mail.utoronto.ca; dsong@chem.utoronto.ca

The direct amination of C-H bonds is an area of great

interest to synthetic chemists1 as a means to access the

wide range of useful molecules with nitrogen-containing

functionalities2. One way to achieve this transformation is

to insert nitrenes into C–H bonds,3 where metal complexes

have been used to stabilize nitrenes and improve the

selectivity.4,5

In this presentation the reactivity of bulky

phenylenediamide (pda) complexes towards organic azides

in nitrene formation and transfer reactions will be

discussed . One example is shown below.

1. Sharma, A.; Hartwig. J. F. Nature., 2015, 517, 600-604.

2. Hili, R.; Yudin, A. K., Nat. Chem. Biol., 2006, 2, 284-287.

3. Egger, J.; Carreira, E. M., Nat. Prod. Rep., 31, 451-453.

4. Hennessy, E. T.; Betley, T. A. Science., 2013, 340, 591-595.

5. Ramirez, T. A.; Zhao, B.; Shi, Y., Chem. Soc. Rev., 2012, 41, 931-942

O22 Solvent Stabilized Dinitrogen Trioxide as a Laboratory Reagent

Kristopher Rosadiuk and D. S. Bohle*

Department of Chemistry, McGill University, Montreal, QC, Canada Kristopher.Rosadiuk@mail.mcgill.ca; Scott.Bohle@mcgill.ca

Dinitrogen trioxide (N2O3) is normally stable only under extremely cold temperatures, and quickly dissociates into NO

and NO2 upon warming. A little known fact is that N2O3 may be stabilized by dissolving it in organic solvents. This

presentation describes the handling of these solutions and explores some of the novel ways that it has been used in our

lab, such as the production of tertiary amine adducts and polymercury salts.

27

O23 Evaluation of Anisole-Substituted Boron Difluoride Formazanate Complexes for

Fluorescence Cell Imaging

Ryan R. Maar, Stephanie M. Barbon, Neha Sharma, Hilary Groom, Leonard G. Luyt, and Joe B. Gilroy*

Department of Chemistry, Western University, London, ON, Canada rmaar@uwo.ca; joe.gilroy@uwo.ca

Fluorescent materials have been known for nearly a century, and are attractive targets for

scientists in research fields such as organic electronics, chemical sensing, and cell imaging.

Much of the research in the field of fluorescent materials has been devoted to four-coordinate

boron compounds with chelating, π-conjugated ligands.1

Recent advances by the Gilroy group

have focused on the synthesis of boron difluoride formazanate complexes (e.g., 1) which were

shown to exhibit tunable spectroscopic and redox properties.2 This presentation will describe a

systematic study designed to probe the effect of ortho-, meta-, and para-substitution patterns

of anisole rings bound to a boron difluoride formazanate scaffold. Based on its

straightforward, high-yielding synthesis and impressive fluorescence quantum yield, 1c was

chosen for fluorescence cell-imaging studies. The structural features, spectroscopic

characteristics and electrochemical properties of 1a−c, and the cell-imaging studies of 1c will

be discussed in detail during this presentation.

(1) Ulrich, G.; Ziessel, R.; Harriman, A. Angew. Chem. Int. Ed. 2008, 47, 1184−1201. (2)

Maar, R. R.; Barbon, S. M.; Sharma, N.; Groom, H.; Luyt, L. G.; Gilroy, J. B. Chem. Eur. J.

2015, DOI: 10.1002/chem.201502821.

O24 Pyrido[2,1-α]-isoindole as a Novel Ligand in Main Group and Transition Metal

Chemistry

Sean M. McDonald and Suning Wang*

Department of Chemistry, Queen’s University, Kingston, ON, Canada

sean.mcdonald@chem.queensu.ca; suning.wang@chem.queensu.ca

Pyrido[2,1-α]-isoindoles have been synthetically accessible since the 1960s.1,2

However, very little investigation has

been made into their reactive capabilities. The majority of work has gone into studying cycloadditions with alkynes to

produce unique and polarized system.3,4

Due to its electronic structure, pyrido[2,1- α]-isoindole has nucleophilic

character at the 6-position, leading to great potential for use as a novel ligand in main group and transition metal

chemistry. The Wang group has already

showcased the adduct formation with

HB(C6F5)2 as an intermediate step towards

1,1-hydroboration.5 This work will detail the

coordination chemistry and novel reactivity

of pyrido[2,1-α]-isoindole with main group

elements and transition metals.

1. Fozard A., Bradsher C. K.; Tetrahedron Lett., 1966, 7, 3341. 2. Fozard A., Bradsher C. K.; J. Org. Chem., 1967, 32,

2966. 3. Kajigaeshi S., Mori S., Fujisaki S., Kanemasa S.; Bull. Chem. Soc. Jpn., 1985, 58, 3547. 4. Mitsumori T.,

Bendikov M., Dautel O., Wudl F., Shioya T., Sato H., Sato Y.; JACS, 2004, 51, 16793. 5. Yang D.-T., Mellerup S. K.,

Wang X., Lu J.-S., Wang S.; Angew.Chem.Int.Ed., 2015, 54, 5498.

28

O25 Bis-Carbene-Stabilized Phosphorus Cations

Justin F. Binder, Ala’aeddeen Swidan, Martin Tang, Jennifer H. Nguyen, and Charles L. B. Macdonald *

Department of Chemistry and Biochemistry, University of Windsor, Windsor, ON, Canada

binderj@uwindsor.ca; cmacd@uwindsor.ca

Phosphamethine cyanine dyes are landmark molecules for main group chemistry in that they provided the first concrete

evidence of 3p-2p π-bonding.1 In spite of this historical relevance, chemistry involving these low-valent phosphorus

compounds remains underexplored. Our group discovered that the reaction between a triphosphenium salt and carbenes

is a safe, convenient route to such species.2 Investigations into their syntheses, properties and reactivity are presented.

1 P. Jutzi, Angew. Chem. Int. Ed., 1975, 14, 232–245.

2 B. D. Ellis, C. A. Dyker, A. Decken and C. L. B. Macdonald, Chem. Commun., 2005, 1965–1967.

O26 Engineered Designer Monomers: The Path to Light and Moisture Stable

Polystannanes

Jeffrey Pau and Daniel Foucher*

Department of Chemistry and Biology, Ryerson University, Toronto, ON, Canada

j2pau@ryerson.ca; daniel.foucher@ryerson.ca

This work continues an investigation into the utility of covalently attached light absorbing chromophores to protect the

light sensitive Sn-Sn backbone of polystannanes. Here the UV absorbing azobenzene “antenna” is incorporated into a

polymerizable tin dihydride monomer that may lead to interesting homo- and copolystannane materials. Additionally,

the flexible nature of the attached UV chromophore is such that it can adopt 5-coordinate geometry at Sn to further

protect the sensitive Sn-Sn polymer bonds from nucleophilic attack. In this work, we present syntheses of azostannyl

compound 5 achieved through a Williamson ether synthesis.

Compound 5 is then sequentially chlorinated to the mono- 6

and dichlorostannane 7. Compound 8 was then obtained by

hydrogenation of 7 with LiAlH4. The azo-stannyl monomer 8

was then reacted with a suitable transition metal catalyst that

promoted dehydropolymerization to the polystannane 9. All

structures were confirmed by NMR (1H,

13C,

119Sn, HSQC)

and in the case of 5 and 6, an X-ray crystal structure analysis.

The UV behaviour of the azo-stannyl compounds were also

probed by UV-Vis spectroscopy. Investigations show that the

cis- (n-p*) and trans- (p-p*) light switching characteristics of

azobenzene are preserved in the stannyl compounds.

29

O27 N-Heterocyclic Carbene Stabilized Ag Nanoparticles

Iraklii I. Ebralidze1 and Heinz-Bernhard Kraatz

1,2*

1Department of Physical and Environmental Sciences, University of Toronto, Scarborough, ON, Canada;

2Department of Chemistry and Chemical Engineering, Royal Military College, Kingston, ON, Canada

iraklii.ebralidze@utoronto.ca; bernie.kraatz@utoronto.ca

Metal nanoparticles (NPs) are a focus of interest because of their unique properties and thus huge potential in science

and engineering. Silver nanoparticles (AgNPs) as well as silver in ionic form, are known to possess antimicrobial

effects. AgNPs are known to interact with heavy metal ions such as Hg(II), Hg(I), Pb(II), and Cd(II) showing significant

growth in size upon their incorporation and therefore can be used for drinking water purification.1 Moreover, silver NPs

can be synthesized and modified with various chemical functional groups which allow them to be conjugated with

antibodies, ligands, and drugs of interest and thus opening a wide range of potential applications in biotechnology,

magnetic separation, and pre-concentration of target analytes, targeted drug delivery, and vehicles for gene and drug

delivery and more importantly diagnostic imaging.2 Even though tremendous number of applications, synthetic routes

for AgNPs are limited to the reduction of Ag+ in presence of stabilizing/capping reagents such as (I) nonionic

surfactants (poly(vinyl pyrrolidone, Triton X-100 ), (II) citrate anions, (III) thiols, or their mixtures. From this list only

thiols form strong bonds with AuNPs and allow further functionalization to achieve desired modern architectures.

Crudden et al.3 have recently shown that thiols anchored to gold surfaces can be substituted by N-heterocyclic carbenes

(NHC) due to formation of much stronger covalent Au-NHC bond. On the other hand, deprotonation of azolium salts

(NHC precursors) using a silver base (or simultaneously a silver salt and a base) has been the most widely used method

in the syntheses of NHC complexes of silver. Taking this into mind, we developed a route of formation of AgNPs

starting from NHC-Ag complexes. This route results in AgNPs stabilized by covalently bounded carbenes.

1. M.S. Bootharaju, T. Pradeep, J. Phys. Chem. C. 114(18), 2010, 8328–8336. 2. V.V. Mody, R. Siwale, A. Singh, H.R.

Mody. J.Pharm. Bioallied Sci. 2(4), 2010, 282-289. 3. Cathleen M. Crudden et al. Nature Chem. 6, 2014, 409–414.

O28 Iterative, Protecting Group Free Suzuki-Miyaura Coupling of Enantioenriched

Polyboronates

C. Ziebenhaus,1 Jason P. G. Rygus,

1 K. Ghozati,

1 P. J. Unsworth,

1 S. Voth,

1 Y. Maekawa,

1 C. M. Crudden,

*,1 and

M. Nambo2

1Department of Chemistry, Queen’s University, Kingston, ON, Canada;

2Nagoya University, Japan

jason.rygus@chem.queensu.ca; cathleen.crudden@chem.queensu.ca

The Suzuki-Miyaura cross-coupling is among the most widely used reactions in

chemical synthesis. In particular, it has found wide applicability in the construction of

biaryl or polyene scaffolds, and has been proposed as the key reaction for the modular,

automated assembly of such structural motifs1. Such a process relies on the use of

protecting groups to modulate the activity of various C-B bonds, and thus requires

costly, inefficient protection and deprotection steps for each bond forming sequence.

Herein we describe a significant advancement in the field of iterative cross-coupling

of polyborylated substrates containing aromatic, primary aliphatic and second

aliphatic C-B bonds2 to generate enantioenriched, multiply arylated structures without

the use of boron protecting groups. We demonstrate chemoselective cross-coupling

based solely on the intrinsic differences in reactivity imparted by the nature of the C-B

bond. 1Woerly E.M., Roy J. & Burke M.D., Nature Chem. 2014, 6, 484

2Imao D., Glasspoole B.W., Laberge V.S. & Crudden C.M. J. Am. Chem. Soc. 2009, 131, 5024

30

O29 Chan-Lam Coupling Using a Copper(II) Complex with a Sulfonated Diketimine

Ligand

Valérie Hardouin Duparc and Frank Schaper*

Département de chimie, Université de Montréal, Montréal, QC, Canada

valerie.hardouin.duparc@gmail.com; frank.schaper@umontreal.ca

Chan-Lam coupling is a well-known cross-coupling reaction between an aryl boronic

acid and an alcohol or an amine in presence of copper(II) to form a C-O or C-N

bond.1 While environmentally friendly and economic, several aspects of Chan-Lam

couplings can still be optimized: reaction conditions often need to be adapted for the

substrate, stoichiometric amounts of copper are sometimes required and presence of

base is normally necessary.2

We recently synthetized copper complexes based on sulfonated

diketimine ligands,3 and studied their structural features and stability. The

obtained complexes were then tested in Chan-Lam coupling and proved to

work under mild condition and to be applicable to a variety of amine

substrates.

1 (a) Chan, D. M. T.; Monaco, K. L.; Wang, R.-P.; Winters, M. P. Tetrahedron Lett. 1998, 39, 2933. (b) Evans, D. A.;

Katz, J. L.; West, T. R. Tetrahedron Lett. 1998, 39, 2937. (c) Lam, P. Y. S.; Clark, C. G.; Saubern, S.; Adams, J.;

Winters, M. P.; Chan, D. M. T.; Combs, A. Tetrahedron Lett. 1998, 39, 2941. 2

(a) Ley, S. V.; Thomas, A. W. Angew. Chem. Int. Ed. 2003, 42, 5400 (b) Allen, S. E.; Walvoord,R. R.; Padilla-Salinas,

R.; Kozlowski, M. C. Chem. Rev. 2013, 113, 6234. 3 Rajendran, N. M.; Reddy, N. D. Polyhedron 2014, 72, 27.

O30 Stable Organopalladium(IV) Aryldiazenido Complexes

David Armstrong,1 Marzieh Daryanavard,

1 Alan J. Lough,

2 and Ulrich W. Fekl

*,1

1University of Toronto Mississauga, Mississauga, ON, Canada;

2University of Toronto, Toronto, ON,

Canada dayv.armstrong@utoronto.ca; ulrich.fekl@utoronto.ca

The usefulness of palladium complexes as catalysts in organic synthesis,

for a range of C-C and C-X coupling reactions, is well recognized.1 The

2010 Nobel Prize in Chemistry was awarded to Heck, Negishi, and

Suzuki for their work on palladium catalyzed cross-coupling reactions.2

Mechanistically, the vast majority of catalytic cycles involve a

Pd(0)/Pd(II) redox couple.1,3

While there have been some recent reports

of the involvement of Pd(III) and Pd(IV)4 in some catalytic cycles, much

less is known about the catalytic potential of Pd(II)/Pd(IV) redox pairs.5

We have demonstrated the synthesis and characterization of the first

palladium(IV) aryldiazenido complexes, formed by the oxidation of

(Tp*)PdMe2 (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) using

aryldiazonium salts. Thermolysis of these compounds leads to substituted

biphenyls via C-C coupling. Synthesis and reactivity will be discussed, as well as implications for palladium catalysis

involving high oxidation states of palladium. 1 Negishi, E. Handbook of Organopalladium Chemistry for Organic Synthesis; John Wiley & Sons: NJ, 2002.

2 http://www.nobelprize.org/nobel_prizes/chemistry/laureates/2010/.

3 (a) van Leeuwen, P. W. N. M. Homogeneous Catalysis: Understanding the Art; Kluwer: The Netherlands, 2004.

4 (a) Lyons, T. W.; Sanford, M. S. Chem. Rev. 2010, 110, 1147. (b) Xu, L.-M.; Li, B.-J.; Yang, Z.; Shi, Z.-J. Chem.

Soc. Rev. 2010, 39, 712. (c) Canty, A. J. Dalton Trans. 2009, 10409. 5 (a) Khusnutdinova, J. R.; Qu, F.; Zhang, Y.; Rath, N. P.; Mirica, L. M. Organometallics 2012, 31, 4627. (b)

Chuang, G. J.; Wang, W.; Lee, E.; Ritter, T. J. Am. Chem. Soc. 2011, 133, 1760.

31

O31 Selective C(sp

2)-O Bond Formation from Palladium Complexes by Using a Green

Oxidant

Ava Behnia, Johanna M. Blacquiere*, and Richard J. Puddephatt

*

Department of Chemistry, Western University, London, ON, Canada

abehnia@uwo.ca; johanna.blacquiere@uwo.ca; pudd@uwo.ca

Palladium-catalyzed cross-coupling reactions have revolutionized the ability to form C–heteroatom bonds as well as C-

C bonds. Generation of oxygen containing compounds via C-O reductive elimination are less common and not well

understood. However, C-O bond forming reductive elimination reactions might be very beneficial for designing more

effective and environmentally benign catalytic reactions where H2O2 is used as oxidant. Recently, Mirica et. al. have

introduced an example of selective C(sp2)-O bond forming reaction from a Pd(IV) complex with a tridentate N-donor

ligand.2

Alternatively, Sanford et. al. observed selective C(sp

3)-O reductive elimination with a Pd complex ligated by a

bidentate N-donor ligand.3

These observations suggest that the nature of the ligand plays a role in controlling selectivity

of the bond forming step. We have targeted a Pd(II) complex with a bidentate N-donor and a hydrocarbon ligand that

can coordinate to the metal center through C(sp2) and C(sp

3) centers. We have treated the Pd(II) complex with different

kinds of oxidants to probe the ability to form stable palladium(IV) complexes or to form new palladium(II) complexes

by sequential oxidative addition/reductive elimination reactions. Use of H2O2 as the oxidant gives a very rare example

of C-O bond formation by oxygen atom insertion into an arylpalladium bond. In our system the Pd-C(sp2) bond is more

reactive than the Pd-C(sp3) bond towards reductive elimination reactions.

(1) Hassan, J.; Sévignon, M.; Gozzi, C.; Schulz, E.; Lemaire, M. Chem. Rev., 2002, 102, 1359. (2) Qu, F.;

Khusnutdinova, J. R.; Rath, N. P.; Mirica, L. M. Chem. Commun., 2014, 50, 3036. (3) Camasso, N. N.; Perez-

Temprano, M. H.; Sanford, M. S. J. Am. Chem. Soc., 2014, 136, 12771.

O32 Tuning the Steric and Electronic Properties of Iron-Based Catalysts Using

Modular Phosphine Moieties

Samantha A.M. Smith, Alan J. Lough, and Robert H. Morris*

Department of Chemistry, University of Toronto, Toronto, ON, Canada samanthaam.smith@mail.utoronto.ca; robert.morris@utoronto.ca

The asymmetric hydrogenation (AH)

of ketones is an efficient method for

producing enantio-enriched alcohols

for the use in industrial processes.i

The last decade has proven that the

use of earth-abundant metals as

opposed to precious metals is viable

for the reduction of polar double

bonds.i-iii

Our group has focused on

the use of iron in catalysis for both

asymmetric transfer hydrogenation

(ATH) and AH.iv

Our most recently

developed third generation catalystsv,vi

are highly efficient for the reduction

of ketones via ATH, but not entirely understood. We became interested in how the steric and electronic properties of the

phosphorus moieties alter catalytic results and thus we will discuss how the systematic modification of the substituents

at one phosphorus alter the catalyst structures and their activities and selectivities.

i R. H. Morris, Acc. Chem. Res. 2015, 48, 1494;

ii Ohkuma, Takeshi, et al. JACS., 2006, 128, 8724;

iii T. Ikariya, A. J.

Blacker, Acc. Chem. Res., 2007, 40, 1300; iv P. E. Sues, K. Z. Demmans, R. H. Morris, Dalton Trans., 43, 2014, 7650;

v

W. Zuo, A. J. Lough, Y. F. Li, R. H. Morris, Science, 2013, 342, 1080; vi S. A. M. Smith, R. H. Morris, Synthesis, 2015,

47, 1775

1940

1945

1950

1955

1960

1965

1970

1975

1980

130 140 150 160 170 180

ν(C

O)

(Cm

-1)

Cone Angle (deg)

32

O33 Intercalation of Coordinatively-Unsaturated Fe

III Ion within Interpenetrated

MOF-5

Rebecca J. Holmberg, Thomas Burns, Samuel M. Greer, Libor Kobera, Sebastian A. Stoian, Ilia Korobkov,

Stephen Hill, David L. Bryce, Tom K. Woo, and Muralee Murugesu

*

Department of Chemistry, University of Ottawa, Ottawa, ON, Canada rholmber@uottawa.ca; m.murugesu@uottawa.ca

Despite the potential that has clearly been displayed by metal substitution within MOF-5, there have not yet been any

examples of metal addition to the structure outside of the Zn4O SBU. This is a worthwhile endeavor, especially

considering the already remarkable improvements to the properties of MOF-5 that have been accessed through simple

metal substitution.1 Thus, we set out to explore the addition of a coordinatively unsaturated Fe

III metal site to the

framework. This new structure, FeIII

-iMOF-5,2 is the first example of an interpenetrated MOF linked through

intercalated metal ions. Structural characterization was performed with single-crystal and powder XRD, followed by

extensive analysis by spectroscopic methods and solid-state NMR, which reveals the paramagnetic ion through its

interaction with the framework. EPR and Mössbauer spectroscopy confirmed that the intercalated ions were indeed FeIII

,

while DFT calculations were employed to ascertain the unique pentacoordinate architecture around the FeIII

ion.

Interestingly, this is also the first crystallographic evidence of pentacoordinate ZnII within the MOF-5 SBU. This new

MOF structure displays the potential for metal site addition as a framework connector, thus, creating further opportunity

for the innovative development of new MOF materials.

1 (a) Botas, J. A.; Calleja, G.; Sanchez-Sanchez, M.; Orcajo, M. G. Langmuir 2010, 26, 5300.; (b) Brozek, C. K.;

Dincă, M. Chem. Sci. 2012, 3, 2110.; (c) Brozek, C. K.; Dincă, M. J. Am. Chem. Soc. 2013, 135, 12886.; (d) Brozek,

C. K.; Miller, J. T.; Stoian, S. A.; Dincă, M. J. Am. Chem. Soc. 2015, 137, 7495.; (e) Brozek, C. K.; Michaelis, V.

K.; Ong, T.-C.; Bellarosa, L.; López, N.; Griffin, R. G.; Dincă, M. ACS Cent. Sci. 2015, 1, 252.

2 Holmberg, R. J.; Burns, T.; Greer, S. M.; Kobera, L.; Stoian, S. A.; Korobkov, I.; Hill, S.; Bryce, D. L.; Woo, T.

K.; Murugesu, M. J. Am. Chem. Soc. 2015, ja-2015-10584t.

O34 Towards Modeling the Active Site of Photosystem II: New Structural Motifs in

Mn/Ca Chemistry from the Use of Salicylhydroxime

Alysha A. Alaimo,1 Simon J. Teat,

2 George Christou,

3 and Theocharis C. Stamatatos*

,1

1Department of Chemistry, Brock University, St. Catharines, ON, Canada;

2Advanced Light Source,

Lawrence Berkeley National Laboratory, Berkeley, CA, USA; 3Department of Chemistry, University of

Florida, Gainesville, Florida, USA aa08mi@brocku.ca; tstamatatos@brocku.ca Toward the synthesis of new structural models of the oxygen-

evolving complex (OEC) within Photosystem II, some of the most

crucial challenges to confront are: (i) the Mn4Ca metal

stoichiometry, (ii) the extended, distorted cubane conformation, (iii)

the stability of high oxidation states for the Mn ions, and (iv) the

choice of the ancillary bridging ligand(s). With this in mind, we

have chosen to employ salicylhydroxamic acid (shaH2, Scheme 1), a photosynthetically

effective group, as a means of obtaining new molecular species containing both Mn

n+

(n>2) and Ca2+

.1 Ligand shaH2 can potentially undergo a metal-assisted amide-iminol

tautomerism, and thus transform to salicylhydroxime (shiH3); the latter is an oximate-

based ligand with four coordination sites available for binding to both high oxidation state

Mn and Ca2+

metal centers. We here present the synthesis, structural, and physicochemical

properties of a series of new heterometallic Mn/Ca complexes with interesting topologies

and novel molecular motifs (Figure).

1 A. A. Alaimo,

D. Takahashi, L. Cunha-Silva,

G. Christou, Th. C. Stamatatos, Inorg.

Chem. 54, 2137, 2015

33

O35 Single Molecule Magnet (SMM)

Munendra Yadav and Scott Bohle *

Department of Chemistry, McGill University, Montreal, QC, Canada Munendra.yadav@mcgill.ca; david.bohle@mcgill.ca

Single Molecule Magnets (SMM) is a class of molecular compounds which shows

supermagnetic behaviour below a certain temperature called as the blocking temperate (TB).

These complexes act as nanomagnets, in which every single molecule behaves like an

independent magnet. The basic requirement to show SMM behaviour is that the complex

should have negative uni-axial magnetic anisotropy (D) and a non zero spin ground state (S).

These two parameters combine to give an energy barrier by which slow relaxation of

magnetization can take place. This energy barrier for integral spin is calculated by Ueff =

│D│S2 and for half integral spin Ueff = │D│(S

2-1/4). The negative uni-axial anisotropy (D ˂

0) removes the degeneracy of ground spin states (MS) = ±S.

Interest in lanthanide ions has been revived and 4f coordination compounds have been

extensively investigated for their single-molecule magnet (SMM) and single-ion magnet

(SIM) properties. The large spin multiplicity and large magnetic anisotropies of

lanthanides ions in the ground state plays a key role to get the SMM behaviour. Strong

single ion anisotropy of lanthanides and flexibility in anisotropy is another advantage by

which it is easy to design the ligand so that it can create the ligand field anisotropy.

Munendra Yadav, Valeriu Mereacre, Sergei Lebedkin, Manfred M. Kappes, Annie K.

Powell, and Peter W. Roesky “Mononuclear and Tetranuclear Compounds of Yttrium and Dysprosium ligated by a

Salicylic Schiff-Base Derivative: Synthesis, Photoluminescence and Magnetism” Inorg. Chem. 2015, 54, 773-781.

O36 Ligand Effects in Copper-Catalyzed Aerobic Oxygenation of Phenols

Laura Andrea Rodríguez Solano,1 Jean-Phlip Lumb,

2 and Xavier Ottenwaelder

1*

1XoRG, Department of Chemistry and Biochemistry, Concordia University, Montreal, QC, Canada;

2Department of Chemistry, McGill University, Montreal, QC, Canada

lanrosol@gmail.com; dr.x@concordia.ca

Tyrosinase is a ubiquitous copper-containing enzyme that converts phenols into ortho-quinones. Its active site contains

two His3-Cu centres that activate O2 in the form of a side-on peroxo dicopper(II) species, P.1 Biomimetic studies have

shown that polyamine ligands can control the reactivity between Cu(I) and O2, favouring different coordination modes

and CunO2 species.2 Recently, the Lumb group reported an efficient tyrosinase-like catalytic system capable of

converting phenols into ortho-quinones under aerobic conditions.4 Our mechanistic study demonstrated the involvement

of a P species in the catalytic cycle.5 The present work showcases systematic variations of the ligand used in this

catalytic system, with 4-tert-butylphenol as model

substrate. We correlate the catalytic efficiency at room

temperature with the nature of the Cu2O2 species forming

at -80°C, and show that only ligands that can

accommodate a P intermediate lead to decent catalysis.

We propose plausible grounds to explain this correlation.

1. Solomon, E. I. et al. Chem. Rev. 114, 3659–3853 (2014).

2. Mirica, L. M., Ottenwaelder, X. & Stack, T. D. P. Chem Rev 104, 1013–1046 (2004).

3. Mirica, L. M. et al. Science 308, 1890–1892 (2005).

4. Esguerra, K. V. N., Fall, Y. & Lumb, J.-P. Angew. Chem. Int. Ed. 53, 5877–5881 (2014).

5. Askari, M. S., Esguerra, K. V. N., Lumb, J.-P. & Ottenwaelder, X. Inorg. Chem. 54, 8665–8672 (2015).

34

O37 1,2-Diphosphonium Dication : A Strong P-Based Lewis Acid in Frustrated Lewis

Pair Activations of B-H, Si-H, C-H and H-H Bonds

Julia M. Bayne, Michael H. Holthausen, Ian Mallov, Roman Dobrovetsky, and Doug W. Stephan *

Department of Chemistry, University of Toronto, Toronto, ON, Canada

julia.bayne@mail.utoronto.ca; dstephan@chem.utoronto.ca

The heterolytic splitting of dihydrogen (H2) by main group frustrated Lewis pairs (FLPs) remains a landmark

achievement in Lewis acid and FLP chemistry. FLPs used for small molecule activation typically exploit boranes,

alanes, or tricoordinate carbon- or silicon-centered cations as main group Lewis acids.1 Exploring electron deficient

compounds of group 15, our group demonstrated the remarkable catalytic activity of the highly electrophilic phosphorus

cation (EPC) [(C6F5)3PF]+ and the phosphonium dication [(SIMes)Ph2PF]

2+ in a variety of Lewis acid-mediated

transformations.2 Although EPCs have been exploited as Lewis acid catalysts, examples of P-based Lewis acids in FLP-

type reactions are scarce. To this end, our group reported the direct activation of H2 with a triphosphabenzene

derivative3 and olefin hydrogenation with the phosphonium cation [(C6F5)3PF]

+ and sterically encumbered aryl amines.

4

In this presentation, the synthesis and reactivity of a robust and highly Lewis acidic 1,2-diphosphonium dication

[(C10H6)(Ph2P)2]2+

will be discussed. In combination with phosphorus Lewis bases, the remarkable hydridophilicity of

this dication was demonstrated through its ability to activate B-H, Si-H, C-H and H-H bonds.5

(1) D. W. Stephan and G. Erker, Angew. Chem. Int. Ed., 2015, 54, 6400-6441. (2) J. M. Bayne and D. W. Stephan,

Chem. Soc. Rev., 2015, DOI: 10.1039/C5CS00516G. (3) L. E. Longobardi et al., J. Am. Chem. Soc., 2014, 136, 13453-

13457. (4) T. vom Stein et al., Angew. Chem. Int Ed., 2015, 54, 10178-10182. (5) M. H. Holthausen, J. M. Bayne, I.

Mallov, R. Dobrovetsky and D. W. Stephan, J. Am. Chem. Soc., 2015, 137, 7298-7301.

O38 Progress in Boro-cation Catalysis for Hydrofunctionalization

Patrick Eisenberger* and Cathleen M. Crudden

*

Department of Chemistry, Queen's University, Kingston, ON, Canada

patrick.eisenberger@chem.queensu.ca; cathleen.crudden@chem.queensu.ca

Cationic, 3-coordinate boron compounds have recently stepped into the limelight as promising non-metal-based Lewis

acidic catalysts for organic synthesis.[1]

Here we present our

progress in catalyst design using meso-ionic carbene-stabilized

borenium as well as DABCO-borenium ions for mild

hydrofunctionalization of unsaturated organic molecules with

hydrogen and borane.[2,3]

Mechanistic investigations suggest

that both these processes occur by distinctly different pathways

involving common motifs of Lewis-base supported borenium-

ions participating in bond activation and Lewis base supported

boranes as the reductant.

[1]

T. S. De Vries, A. Prokofievs, E. Vedejs Chem. Rev. 2012,

112, 4246. [2]

P. Eisenberger, A. M. Bailey, C. M. Crudden J.

Am. Chem. Soc. 2012, 134, 17384. [3]

P. Eisenberger, B. P.

Bestvater, E. C. Keske, C. M. Crudden Angew. Chem. Int. Ed. 2015, 54, 2467.

35

P1 Complexation of Fe(II) and Fe(III) with the Tau Protein

Soha Ahmadi,1,2

Iraklii I. Ebralidze,1 Zhe She,

1 and Heinz-Bernhard Kraatz

*1,2

1Department of Physical and Environmental Sciences, University of Toronto Scarborough, Toronto, ON,

Canada; 2Department of Chemistry, University of Toronto, Toronto, ON, Canada

soha.ahmadi@mail.utoronto.ca; bernie.kraatz@utoronto.ca

Tau is a protein that is associated with the stabilization of microtubules. A number of isoforms have been described in

the literature and all have binding domains that bind to microtubules. (1) Hyperphosphorylation of tau catalyzed by

protein kinases disrupts the interaction between tau and the microtubules, which in turn destabilizes the tubules leading

to decomposition into their building blocks a- and b-tubulins. (2) Hyperphosphorylation of tau then leads to aggregation

and formation of neurofibrillary tangles, one of the hallmarks of Alzheimer’s disease. Metal ions appear to play a vital

role and experimental results have shown increased levels of Fe, Cu, and Zn are associated with neurofibrillary tangles.

(3) Previously we have demonstrated that Cu(II) and Zn(II) can interact with tau and with phosphorylated tau (p-tau)

(4). Here we investigate the interaction of Fe(II) and Fe(III) with tau, p-tau and fragment peptides in an effort to further

our understanding of metal-tau interactions.

1. Frost, B., Götz, J., Feany, M.B. Connecting the dots between tau dysfunction and neurodegeneration . 2015, 25, 46-

53;

2. Krüger, .L; Mandelkow, E.M. Tau neurotoxicity and rescue in animal models of human Tauopathies. Current

Opinion in Neurobiology. 2016, 36, 52-58;

3. Ayton S., Lei P., Bush A.L. Biometals and Their Therapeutic Implications in Alzheimer’sDisease. Neurotherapeutics.

2015, 12, 109-120;

4. Martic, S.; Rains, M. K.; Kraatz, H.-B. Probing copper/tau protein interactions electrochemically. Anal. Biochem.

2013, 442, 130-137

P2 New Classes of Ferromagnetic Materials with Exclusively End-on Azido Bridges:

From Single- to 2D- Molecular Magnets

Dimitris I. Alexandropoulos,1 Luís Cunha-Silva,

2 Albert Escuer,

3 and Theocharis C. Stamatatos

*1

1Department of Chemistry, Brock University, St. Catharines, ON, Canada;

2REQUIMTE & Department of

Chemistry and Biochemistry, Faculty of Sciences, University of Porto, Porto, Portugal; 3Departament de

Quimica Inorganica, Universitat de Barcelona, Barcelona, Spain da12he@brocku.ca; tstamatatos@brocku.ca

A new, flexible synthetic route which does not require the co-presence of any organic

chelating/bridging ligand but only the “key” precursor Me3SiN3 has been discovered

and led to a new class of inorganic materials bearing exclusively end-on azido bridges;

the reported 3d-metal clusters and coordination polymers exhibit ferromagnetic,

single-molecule magnetism (Figure) and long-range magnetic ordering properties.1

[1] D. I. Alexandropoulos, L. Cunha-Silva, A. Escuer, and Th. C. Stamatatos, Chem

Eur. J., 2014, 20, 13860.

Figure. χM'' vs. T plot for a [CoII7]

complex discussed in this work.

36

P3 Synthesis and Characterization of a Family of [ReBr(CO)3(NN)]-Polyoxometalate

Covalent Hybrids

Thomas Auvray, Marie-Pierre Santoni, and Garry Hanan*

Département de chimie, Université de Montréal, Montréal, QC, Canada thomas.auvray@umontreal.ca; garry.hanan@umontreal.ca

The elaboration of hybrid systems combining the

intrinsic properties of its subcomponents is a widely

used approach in modern chemistry. Being interested

in the design of efficient light harvesting species to

convert solar energy into chemical energy, we decided

to combine the well-known [Re(CO)3Br(bpy)]

photosensitizer with polyoxometalates, a family of

anionic oxoclusters known for its electron reservoir

properties.1 A family of polypyridine ligands

covalently grafted on a Dawson type polyoxometalate

and its use as ligands to prepared the corresponding

Re(I) complex is presented.

1 M.-P. Santoni et al. , Dalton Trans., 2014, 43, 6990-

6993

P4 Characterization of Cross-Coupling Reactions of Simple Iron Salts with Phenyl

Nucleophiles

Stephanie H. Carpenter and Michael L. Neidig*

Department of Chemistry, University of Rochester, Rochester, NY, USA scarpen7@ur.rochester.edu; neidig@chem.rochester.edu

Iron-catalyzed C-C cross-coupling systems have been known since the 1970s1, yet there is limited mechanistic

understanding of these systems. Simple iron salts are inexpensive and nontoxic, and are known to have short reaction

times and mild reaction conditions. Hence, simple iron salts are attractive starting materials for cross-coupling systems.

Previous work in the group involves the isolation and characterization of a homoleptic tetramethyliron(III) ferrate

complex from catalytically relevant iron salt, solvent, and methylmagnesium bromide. Further studies showed the

homoleptic tetramethyliron(III) ferrate complex to be an intermediate in the reduction pathway of FeCl3 and MeMgBr.

Current efforts are being placed on the isolation of intermediates formed during the reaction from simple iron salts and

various phenyl nucleophiles. Electron paramagnetic resonance (EPR) and Mössbauer spectroscopy have shown the

intermediates formed from simple iron salts and phenyl nucleophiles to be different from the methyl reduction pathway.

1. Tamura, M.; Kochi, J. K. J. Am. Chem. Soc. 1971, 93, 1487.

2. Al-Afyouni, M. H.; Fillman, K. L.; Brennessel, W. W.; Neidig, M. L. J. Am. Chem. Soc. 2014, 136, 15457.

37

P5 d

10 Nickel Difluorocarbenes and their Cycloaddition Addition Reactions with

Tetrafluoroethylene

Alex L. Daniels, Daniel J. Harrison*, Ilia Korobkov, and R. Tom Baker

*

Department of Chemistry, University of Ottawa, Ottawa, ON, Canada adani088@uottawa.ca; dharris2@uottawa.ca; rbaker@uOttawa.ca

We report the first isolable nickel difluorocarbene complexes {NiP2[P(OMe)3](=CF2); P2 = Ph2P(CH2)2PPh2 (1); P2 = 2

P(OMe)3 (2)}, which are also the only examples of formally d10

metal fluorocarbenes. These electron-rich [Ni0]=CF2

complexes react with tetrafluoroethylene (TFE) to yield rare perfluorometallacyclobutanes [NiP2(κ2-CF2CF2CF2-), 3 and

4], with potential relevance to fluoroalkene metathesis and polymerization. Kinetic experiments establish that the

reactions of the new [Ni]=CF2 compounds with TFE are considerably faster than the analogous reactions of their

previously reported [Co]=CF2 counterparts. Further, we show that TFE addition to 2 is a dissociative process, in

contrast to [Co]=CF2, which reacts with TFE in an associative fashion. Finally, preliminary reactivity of a [Ni](κ2-

CF2CF2CF2-) complex (3) is described.

P6 Exploring the Water-Tolerance of Ruthenium Metathesis Catalysts

Adrian G. G. Botti and Deryn E. Fogg*

University of Ottawa, Centre for Catalysis Research and Innovation, Ottawa, ON, Canada abott010@uottawa.ca; deryn.fogg@uottawa.ca

The dominant catalysts in current use for olefin metathesis are “second-generation” catalysts bearing an N-heterocyclic

carbene (NHC) ligand, particularly the Grubbs and Hoveyda catalysts (Chart 1). These catalysts are widely regarded as

tolerant toward air and moisture. Indeed, Cazin and co-workers recently reported that turnover numbers up to 7,000

could be attained in non-degassed solvents in RCM of a 1,1-disubstituted olefin using HII.1 On deliberate addition of

water, however, maximum conversions were halved. Here we explore the basis of this behaviour, for both GII and HII.

Specifically, we describe the impact of added water on catalytic productivity with a more typical, ,-vinylic substrate;

we examine reactions of the off-cycle species (precatalyst and resting state; Chart 1) and active catalysts with water,

with a particular focus on the nature of the side-products generated. Finally, we also explore the stability of Ruthenium

species potentially generated via reactions with water.

Chart 1. (a) The dominant olefin metathesis catalysts; (b) Mechanism highlighting key catalytic species studied for GII.

[1] S. Guidone, O. Songs, F. Nahra, C. S. J. Cazin, ACS Catal. 2015, 5, 2697-2701.

(a) (b)

38

P7 The Synthesis and Coordination Chemistry of 3,3’-Disubstituted-2,2’-Bipyridine

Ligands – Dimers, Trimers, Tetramers, and 1-D Chains

Marnie Edwardson, Nicholas J. Hurley, and Melanie Pilkington*

Department of Chemistry, Brock University, St. Catharines, ON, Canada me10wm@brocku.ca; mpilkington@brocku.ca

Bipyridines are a unique class of compounds that are very prevalent in the fields of surpramolecular and coordination

chemistry. Out of six possible regioisomers, 2,2’-bipyridine ligands are the most exploited. However, examples of 3,3’-

disubstituted-2,2’-bipyridines are less common and have not yet realized their full potential in the field of coordination

chemistry to date1.

In recent years we have pursued the synthesis and coordination chemistry of polydentate 3,3’-substituted-2,2’-pyridine

ligands (1)2 and (2)

3 with appended pyridine and pyrazine heterocycles respectively. More recently we have targeted the

preparation of a new ligand (3) with appended oxadiazole-pyridyl heterocycles. The preparation of these ligands

together with magnetostructural studies of selected coordination complexes will be presented.

1 C.R. Rice, S. Onions, N. Vidal, J.D. Wallis, M.C. Senna, M. Pilkington, & H. Stoeckli‐Evans, Eur. J. Inorg.

Chem. 2002, 8, 1985-1997,2 N.J. Hurley, J.J. Hayward, J.M. Rawson, M. Murrie, & M. Pilkington, Inorg. Chem. 2014,

53, 8610-8623, 3 N.J. Hurley, J.M. Rawson, & M. Pilkington, Dalton Trans. 2015, 44, 1866-1874.

P8 Synthesis and Reactivity of Phosphinimine Phosphine Staudinger Products

Louie Fan and Doug W. Stephan*

Department of Chemistry, University of Toronto, Toronto, ON, Canada louie.fan.09.chem@gmail.com; dstephan@chem.utoronto.ca

Frustrated Lewis pairs (FLP) have gained significant attention in the chemical community for their use in the metal-free

activation of small molecules, such as H2, CO2, and NO. The premise for Lewis bases and Lewis acids to have weakly

or nonbonding interactions has been thoroughly investigated in both inter-

and intramolecular FLP systems. Recently, our group reported the reactivity

of various phosphinimine borane1 and borenium

2 Staudinger derived

products for FLP-type chemistry.

In this work, borane-stabilized phosphorus azide, iPr2P(BH3)N3, is reacted

with a series of phosphorus alkynes, R1

2PCCR2 (R

1 = t-Bu, iPr, Ph, R

2 = Ph,

Cy, t-Bu), to generate a family of new phosphinime phosphine products

(Fig. 1). The preparation, characterization and reactivity of a series of

phosphinimine phosphine Staudinger products are explored herein.

1R.L. Melen, A.J. Lough, D.W. Stephan,; Dalton Trans., 42, 8674-8683.

2M.H. Holthausen, I. Mallov, D.W.

Stephan,; Dalton Trans., 43, 15201-15211.

39

P9 Study of Bis-peptide Derivatives of Ferrocenoyl Histidine Including

Electrochemical and Metal Ion Binding Studies

Annaleizle Ferranco and Heinz-Bernhard Kraatz*

Department of Physical and Environmental Sciences, University of Toronto Scarborough, Toronto, ON, Canada annaleizle.ferranco@mail.utoronto.ca; bernie.kraatz@utoronto.ca

Zinc ions are essential for a variety of biological functions in proteins. In some case, Zn(II) plays a structural role, while

in others, it is the active site for a substrate transformation (references please). The most prevalent structural motif has

the Zn(II) in a tetrahedral coordination environment, ligated to the imidazole N in His, the thiolate S in Cys or to

carboxylate ligands of Asp or Glu. Research here focuses on the design of models for Zn-proteins and other

metalloproteins, where the ferrocene group is exploited as a structural scaffold that provides structural rigidity for

peptide residues and forces them into a conformation that is beneficial for metal coordination. Here we focus on the use

of His conjugates of ferrocene and the interaction of several ferrocenoyl histidine peptides was investigated with a

variety of divalent metal ions. Fc-peptide conjugates Fc[CO-His(Trt)-His(Trt)-OMe]2, Fc[CO-His(Trt)-Glu(OMe)-

OMe]2, and Fc[CO-His(Trt)-Glu(OMe)-OMe]2 were synthesized and observed to bind with metal ions Zn2+

, Cd2+

, Cu2+

,

Ni2+

, Mn2+

, and Mg2+

in a 1:1 ratio. Interactions were monitored by 1H NMR spectroscopy and by ESI-TOF-MS.

1. Rebilly, J.-N.; Colasson, B.; Bistri, O.; Over, D.; Reinaud, O. Chem. Soc. Rev. 2015, 44, 467-489.

2. Daniel, A. G,; Farrell, N.P. Metallomics, 2014, 6, 2230-2241.

3. Laitaoja, M.; Valjakka, J.; Jänis, J. Inorg. Chem. 2013, 52, 10983-10991.

P10 Old Dog, New Tricks: Developing the Coordination Chemistry of

2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (TPymT)

Jamie M. Frost, Amélie Pialat, Damir A. Safin, and Muralee Murugesu*

Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, ON, Canada jfrost@uottawa.ca; m.murugesu@uottawa.ca

Owing to the presence of three fused terpyridine-like coordination pockets, 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine

(TPymT, Figure 1 left) is a highly attractive ligand for the synthesis of discrete clusters, coordination polymers and

Metal-Organic Frameworks (MOFs). Despite its potential, the coordination chemistry of TPymT is vastly

underdeveloped – which can principally be attributed to the

hydrolysis of the central triazine fragment, which readily

occurs under mild conditions. Thus, after first being

synthesised in 1959 it had only been used a handful of

times to synthesise coordination compounds until our

group began reinvestigating its chemistry in 2013.[1]

This

poster details our recent progress in developing the

coordination chemistry of TPymT, with a particular focus

on Ag+ (Figure 1 right) and Fe

2+/Fe

3+ chemistry.

See; E. I. Lerner and S. J. Lippard, J. Am. Chem. Soc., 1976, 98, 5397; E. I. Lerner and S. J. Lippard, Inorg.

Chem., 1977, 16, 1537 and A. M. Garcia, D. M. Bassani, J.-M. Lehn, G. Baum and D. Fenske, Chem. Eur. J.,

1999, 5, 1234.

Figure. 1 Molecular structure of TPymT (left) and a

[Ag9TPymT4]9+

segment (right).

40

P11 Initial Employment of 3-Hydroxy-2-naphthohydroxamic Acid

in Mn and Mn/Dy Cluster Chemistry

Dimosthenis P. Giannopoulos,1 Luis Cunha-Silva,

2 George Christou,

3 and Theocharis C. Stamatatos

*,1

1Department of Chemistry, Brock University, St. Catharines, ON, Canada;

2REQUIMTE & Department of

Chemistry and Biochemistry, Faculty of Sciences, University of Porto, Porto, Portugal; 3Department of

Chemistry, University of Florida, Gainesville, Florida, USA dg12eo@brocku.ca; tstamatatos@brocku.ca

The continuing interest in the synthesis and study of high-nuclearity transition

metal clusters in moderate-to-high oxidation states is driven by their

potentially interesting magnetic properties, including high-spin ground state

values (S) and single-molecule magnetism (SMM) behaviors.[1]

Our group, and

others, has also had a longstanding interest in the synthesis of heterometallic

3d/4f SMMs, hoping that the co-presence of two different anisotropic and

high-spin metal ions within the same species will lead to SMMs with

unprecedented structural motifs, large energy barriers for the magnetization

reversal and blocking temperatures shifted to the liquid N2 temperature

regime.[2]

Towards this end, we turned our attention to the multidentate

chelating/bridging organic ligand 3-hydroxy-2-naphthohydroxamic acid

(nhaH2), a bulkier derivative of salicylhydroxamic acid, which has already

been successfully employed in 3d and 3d/4f metal cluster chemistry.[3]

Herein,

we shall discuss our first results from the use of nhaH2 in Mn and Mn/Dy

cluster chemistry (Figure).

[1] G. Aromi and E. K. Brechin, Struct. Bonding (Berlin) 1997, 88, 1.

[2] Th. C. Stamatatos, S. J. Teat, W. Wernsdorfer and G. Christou, Angew. Chem. Int. Ed. 2009, 48, 521.

[3] M. R. Azar, T. T. Boron, J. C. Lutter, C. I. Daly, K. A. Zegalia, R. Nimthong, G. M. Ferrence, M. Zeller, J. W.

Kampf, V. L. Pecoraro and C. M. Zaleski, Inorg. Chem. 2014, 53, 1729.

P12 Rhenium and Ruthenium Complexes as Antibiotics Against Methicilin-Resistant

Staphylococcus Aureus (MRSA)

Anissa Brahami,a Baptiste Laramée-Milette,

b Éric Déziel,

a,* Garry Hanan

b,* and Annie Castonguay

a*

aINRS-Institut Armand-Frappier, Laval, QC, Canada;

bUniversité de Montréal, Montreal, QC, Canada.

anissa.brahami@iaf.inrs.ca; eric.deziel@iaf.inrs.ca, garry.hanan@umontreal.ca, annie.castonguay@iaf.inrs.ca

Antibiotic resistance is a serious and growing phenomenon in contemporary medicine, and a primary public health

concern. Unfortunately, antibiotics are no longer the magic bullets that they once were. New resistance mechanisms

have emerged, making generations of antibiotics virtually ineffective, resulting in prolonged illness, greater risk of death

and higher costs. Thus, development of new antibiotics and other novel strategies are critically needed to overcome the

problems associated with antibiotic resistance. Transition metal complexes have unique properties, notably due to their

partially filled d-orbitals, and can lead to the discovery of antimicrobials that display novel modes of action and

interactions with biomolecules. In this presentation, preliminary results regarding the antibiotic activity of various

rhenium and ruthenium complexes bearing carbon monoxide and terpyridine-type ligands, against methicilin-resistant

Staphylococcus aureus (MRSA), will be reported.

OH

C

O

N

H

OH

3-hydroxy-2-naphthohydroxamic acid (nhaH2)

Figure. (top) The ligand nhaH2, and (bottom) the

structure of a [MnIII8Dy2] cluster.

41

P13 Reactivity of Neutral Ligands Toward the Alkylidene Moiety of Grubbs-type

Olefin Metathesis Catalysts

Faidh Hana, Timothy G. Larocque, Anna C. Badaj, and Gino G. Lavoie*

Department of Chemistry, York University, Toronto, ON, Canada hfaidh@yorku.ca; glavoie@yorku.ca

Ruthenium alkylidene complexes are at the forefront of catalyst research due to the broad scope of possible olefin

metathesis transformations and substrates, including those with polar and protic functional groups. Studies of

decomposition pathways of these complexes are vital for designing catalysts with improved efficiency and lifetime.

Herein we discuss the sensitivity of the Ru=CHR active group to intramolecular insertions from “spectator” ligands. The

effect of the charge in ruthenium alkylidene complexes and the role of strong σ-donor weak π-acceptor phosphaalkenes

were investigated independently. Upon treatment of ruthenium alkylidene complex 1 with AgPF6, dicationic ruthenium

complex 2 was produced through nucleophilic attack from the N-heterocyclic carbene.1 Reaction of phosphaalkene 3

with RuCl2(PCy3)2(CHPh) produced complex 4, which also results from a migratory insertion of the phosphaalkene into

the benzylidene followed by two C-H activation.2 These findings provide important insights for designing the next

generation of ruthenium-based olefin metathesis catalysts.

(1) Larocque, T. G.; Badaj, A. C.; Lavoie, G. G. Dalton Trans. 2013, 42, 14955–14958.

(2) Larocque, T. G.; Lavoie, G. G. New J. Chem. 2014, 38, 499.

P14 Ring-Size Effects on Structures and Properties of Benzo-fused Dithiazolyl

Radicals

Mohamad Harb, Natalia Mroz, Yassine Beldjoudi, and Jeremy Rawson*

Department of Chemistry and Biochemistry, University of Windsor, Windsor, ON, Canada harbm@uwindsor.ca; jmrawson@uwindsor.ca

Sulfur-nitrogen free radicals have been developed in the design of both organic

magnets and conductors. This poster will examine the effects of increasing the ring

size (n = 1 – 3) on a series of benzo-fused dithiazolyls (1). The synthetic

methodology, structures and magnetic properties of these derivatives will be

discussed.

1

( )n .

42

P15 Base Metal and Ruthenium Catalysts for the Synthesis of 1-butanol via the

Guerbet Reaction

Cassandra E. Hayes,1,2

R. Tom Baker,1*

and William D. Jones2*

1Department of Chemistry, University of Ottawa, Ottawa, ON, Canada;

2Department of Chemistry,

University of Rochester, Rochester, NY, USA chayes8@ur.rochester.edu; rbaker@uottawa.ca; wjones@ur.rochester.edu

The development and widespread use of biofuels as replacements for traditional petrochemical fuels is an important and

growing issue to the global economy and environment. Current technologies cite ethanol as the most accessible

renewable fuel source; however, its use comes with a significant list of drawbacks. As such, ready access to so called

“advanced biofuels” (e.g. n-butanol) has become a topic of increasing interest to researchers. The homologation of

ethanol via the Guerbet process (figure) provides a renewable means of accessing n-butanol. Herein we demonstrate the

use of iron, cobalt, and ruthenium

dehydrogenation catalysts for their use

in the Guerbet process. Initial catalytic

studies show that iron and cobalt

catalysts catalyse the Guerbet reaction

with a high selectivity for the formation

of n-butanol over other longer chain by-

products.

P16 Synthesis and Characterization of Heteroleptic Copper(I) Complexes

for Light Harvesting Applications

Jennifer Huynh, Paloma Prieto, Jeanette A. Adjei, and Bryan D. Koivisto*

Department of Chemistry and Biology, Ryerson University, Toronto ON, Canada jennifer3.huynh@ryerson.ca; bryan.koivisto@ryerson.ca

The dye sensitized solar cell (DSSC, or Grätzel cell) is a next generation photovoltaic device that shows remarkable

potential for solar energy markets. The powerhouse of the DSSC is the dye molecule, which has the ability to harvest

light, and convert it into electrical current. Inorganic dyes such as zinc porphyrins and ruthenium(II) complexes have

drawn much attention for their high efficiencies, but heteroleptic tetrahedral copper(I) complexes are a viable alternative

owing to their substantially lower cost and opportunity for development. The main challenge for using tetrahedral Cu(I)

dyes is their energetically favourable distortion to a square planar Cu(II) geometry upon oxidation. To prevent this,

phenanthroline-based ligands are particularly attractive due to their rigid bidentate structure, while functionalizing at the

2,9- positions on the phenanthroline ligand creates a steric environment preventing geometric distortion (Figure 1). This

presentation will focus on recent efforts towards the synthesis and characterization of novel ligands and heteroleptic

copper(I) complexes for light-harvesting applications.

Figure 1. Targeted motif of the Cu(I) complex dye molecule explored in this study.

43

P17 Inclusion Chemistry of 4-Phenyl-1,2,3,5-Dithiadiazolyl Radical in MIL-53(Al)

Erika M. Haskings and J.M. Rawson*

Department of Chemistry and Biochemistry, University of Windsor, Windsor, ON, Canada hasking@uwindsor.ca; jmrawson@uwindsor.ca

The interactions and applications of host-guest chemistry have generated considerable interest in recent years, with the

nature of the host···guest interaction leading to effects in which the host can modify the guest properties or reactivity or,

conversely, the guest affects the host structure. This poster will describe the inclusion chemistry of 4-phenyl-1,2,3,5-

dithiadiazolyl (PhDTDA) radical in the host metal-organic framework MIL-53(Al).

DTDA radicals tend to dimerise in the solid state but undergo monomer-dimer equilibria in solution. In this context we

have been interested to examine how the host affects the monomer-dimer equilibrium and chemical reactivity of the

radical. The PhDTDA radical was incorporated into the porous framework via gas phase diffusion and led to a colour

change of the host from white to red. Powder X-ray diffraction studies and DSC studies

revealed that the radical was included into the framework while solid state EPR studies

indicated low radical concentrations indicating a dimerization can occur within the host

cavities. The reactivity of the radical within the host-guest framework will be discussed.

Figure 1: 4-Phenyl-1,2,3,5-dithiadiazolyl (PhDTDA) radical

P18 Design and Synthesis of Lanthanide Single Molecule Magnets using the Schiff

Base Approach

Thomas Lacelle, Gabriel Brunet, Amélie Pialat, Rebecca J. Holmberg, Wolfgang Wernsdorfer, Ilia Korobkov, and

Muralee Murugesu*

Department of Chemistry, University of Ottawa, Ottawa, ON, Canada tlace071@uottawa.ca; m.murugesu@uottawa.ca

Isostructural complexes of the formula [Ln4(H2htmp)4(MeOH)8](NO3)3(OH)·5MeOH·0.5H2O (Ln = GdIII

1, DyIII

2)

were synthesized using a new Schiff base ligand, abbreviated H4htmp. Compound 2 exhibits ferromagnetic exchange

coupling under zero dc field with a large thermal relaxation barrier of Ueff = 158 K. To the best of our knowledge this

barrier is the sixth largest reported barrier for Schiff base complexes to date. The effect of the bridging tetrazine ring on

the magnetic exchange interactions is explored through structural and magnetic studies.

44

P19 Covalent Organic Frameworks: Using 2D Rigid Cores for Enhanced

Electron/Charge Transport

Andrew Hollingshead, François Magnan, and Jaclyn Brusso*

Department of Chemistry, University of Ottawa, Ottawa, ON, Canada aholl097@uottawa.ca; jbrusso@uottawa.ca

Covalent Organic Frameworks (COFs) represent a relatively new class of crystalline porous materials that have emerged as

a novel strategy in the design of new functional materials. This may be attributed to their atomically precise integration of

building blocks into 2D or 3D topologies, which are characterised by lightweight elements, strong covalent bonds, high

specific surface area, defined pore size and great structural diversity. As a result, since the first reported COF in 2005,1 a

great deal of research has focused on their development for use in a variety of applications such as catalysis, gas storage,

drug delivery, chemical sensing and organic electronics. In regards to the later, the designability of building blocks to

develop robust porous networks that feature 2D extended organic sheets with

layered stacking structures in which periodic columnar π-arrays and

ordered 1D channels are generated is particularly attractive. Our

approach to COFs involves the use of heteroaromatic building blocks

where the π-conjugation can be extended through various aromatic

“linkers” (e.g. benzene vs. naphthalene vs. anthracene). This extension of π-

conjugation is anticipated to enhance the charge transport properties while

creating a new family of semi-conductive materials. Preliminary work

towards the development of monomers 1 and 2, and their

implementation into COFs, will be presented.

1. Cote, A. P.; Benin, A. I.; Ockwig, N. W.; O'Keeffe, M.; Matzger, A. J.; Yaghi, O. M., Science 2005, 310 (5751), 1166-

1170.

P20 Reactivity of Iron Complexes of a Radical o-Phenylenediamine-based Ligand

Trevor Janes, Pavel Zatsepin, and Datong Song*

Department of Chemistry, University of Toronto, Toronto ON, Canada tjanes@chem.utoronto.ca; dsong@chem.utoronto.ca

One of inorganic chemistry’s current goals is to exploit the ability of certain ligands to exist in multiple oxidation states.

Ideally, such ligands will work in concert with metals to accomplish challenging multielectron redox transformations. In

particular, o-phenylenediamine-derived ligands have received attention for their capability as

electron reservoirs.1 Our research group has investigated the coordination chemistry of a

sterically bulky o-phenylenediamide (L2-

) towards Fe2+

; we have observed its readiness to

oxidize into the o-diiminosemiquinonate (L-) form depicted in Figure 1.

2 This poster

presentation will detail our application of the π-delocalized radical L- as a spectator ligand to

sponsor redox processes, facilitate N-group transfer, and stabilize three-coordinate iron.

Figure 1. Bulky o-diiminosemiquinonate (L-)

1. Broere, D. J., Plessius, R., van der Vlugt, J. I., Chem. Soc. Rev., 2015, 44, 6886-6915.

2. Janes, T., Rawson, J. M., Song, D., Dalton Trans., 2013, 42, 10640-10648.

45

P21 Asymmetric Hydrogenation by NHC-stabilized Borenium Ion Catalysis

Jolie Lam and Douglas W. Stephan*

Department of Chemistry, University of Toronto, Toronto, ON, Canada jolie.lam@mail.utoronto.ca; dstephan@chem.utoronto.ca

Amines and their derivatives are synthetically

important compounds with a wide range of

applications, varying from dyes to pharmaceuticals.

In particular, potential pharmaceutical

intermediates and targets are required in high

enantiopurity, which is typically achieved by chiral

transition metal-mediated transformations.1 N-

heterocyclic carbene (NHC)-stabilized borenium

ions2 have recently been reported to be excellent

metal-free catalysts for the hydrogenation of

imines under mild conditions by Stephan and coworkers. We are now targeting the syntheses of new borenium ions that

incorporate chiral substituents for the enantioselective hydrogenation of prochiral imines. Borenium cations stabilized by

chiral bisoxazoline3 carbenes were synthesized and preliminary results show excellent catalysis with high conversions.

Simultaneously, we are tuning the Lewis acidity and selectivity of these systems by exploiting variations of the borane to

enhance reactivity.4 The efficacy of these systems in the asymmetric catalytic reduction of ketimines will be discussed.

1. Fleury-Brégeot, N.; Fuente, V.; Castillón, S.; Claver, C. ChemCatChem. 2010, 2, 1346-1371.

2. Farrell, J. M.; Hatnean, J. A.; Stephan, D. W.. J. Am. Chem. Soc. 2012, 134, 15728-15731.

3. Lindsay, D. M.; McArthur, D. Chem. Commun. 2010, 46, 2474-2476.

4. Farrell, J. M.; Posaratnananthan, R. T.; Stephan, D. W. Chem. Sci. 2015, 6, 2010-2015.

P22 1,1'-biphenyl-4,4'-diamonium bis[trifluoridostannate(II)]

(C10H12N2 2+

, 2SnF3−)

G. Dénès1, *

, A. Muntasar1 , T.N. Mouas

2, S. Boufas

2 and H. Merazig

2

1Laboratory of Solid State Chemistry and Mössbauer spectroscopy, Department of Chemistry and

Biochemistry, Concordia University, Montreal, QC, Canada; 2Laboratoire de Chimie Moléculaire, du

Contrôle de l'Environnement et de Mesures Physico-Chimiques, Département de Chimie, Faculté des Sciences, Université des frères Mentouri de Constantine, Constantine, Algeria, madenes@videotron.ca; hmerazig@gmail.com

Tin(II) organic-inorganic hybrid compounds are very rare. The only structural reports show that the compounds contain the

trifluorostannate(II) SnF3- ion. In the work presented here, the title compound was prepared upon reaction of SnF2 and

benzidine in an H2O/HF solution at 80 oC. The crystal structure showed that, in contrast with the know fluorostannate(II)

hybrids, tin(II) is tetracoordinated. The electron pair geometry around tin is trigonal bipyramidal, while the molecular

geometry is see-saw, with the stereoactive tin lone pair being located on one of the equatorial positions, in agreement with

the VSEPR model of Gillespie and Nyholm. Each SnF4 unit is linked to two neighbors through bridging axial fluorine

atoms, to form infinite chains aligned parallel to one another to form corrugated sheets, with the tin lone pairs all pointing

perpendicularly to the tin sheets, forming sheets of lone pairs, resulting highly efficient cleavage planes. The large isomer

shift (δ = 3.016 mm/s) and quadrupole splitting (Δ = 1.825 mm/s) are expected for a tin(II) with a highly stereoactive lone

pair and bonded to fluorine.

46

P23 Nickel(Ⅱ) and Palladium(Ⅱ) Complexes of Perimidine-based Carbene Ligands:

Catalysis for C-N Coupling

Sojung Lee, T.-G. Ong, E. Perron, I. Korobkov, and Darrin Richeson*

Department of Chemistry, University of Ottawa, Ottawa, ON, Canada slee228@uottawa.ca; darrin@uottawa.ca

The discovery of stable diaminocarbenes as well as their application as ligands for transition metals has had a tremendous

impact on the field of homogeneous catalysis. In this regard, we have designed novel perimidine-based diaminocarbenes as

ligands. These ligands have unique steric and electronic features. The Nickel (0), Nickel(Ⅱ) and Palladium(II) complexes

of these carbene ligands have been synthesized and details of their characterization will be presented. Our initial efforts to

exploit the unique properties of these carbenes and to reveal their potential in metal catalyzed transformations will be

described. For example, the Ni complexes have been found to have oxidative addition of aryl iodide and fluorinated

pydridine and the Pd complexes are active catalysts for C-N bond formation.

P24 Novel Methods of Preparations of Barium Tin(II) Fluorides by Leaching of

Chloride Fluorides in Water

G. Dénès1, *

, A. Muntasar1 , and H. Merazig

2

1Laboratory of Solid State Chemistry and Mössbauer spectroscopy, Department of Chemistry and

Biochemistry, Concordia University, Montreal, QC, Canada; 2Laboratoire de Chimie Moléculaire, du

Contrôle de l'Environnement et de Mesures Physico-Chimiques, Département de Chimie, Faculté des Sciences, Université des frères Mentouri de Constantine, Constantine, Algeria, madenes@videotron.ca; muntsab@gmail.com

Preparations of BaSn2F6 and high performance fluoride conductor BaSnF4 were previously carried by precipitation from

aqueous solutions of tin(II) fluoride and barium nitrate for BaSn2F6 and by high temperature reaction of SnF2 and BaF2

under inert atmosphere for BaSnF4. We have carried out an extensive study of barium tin(II) chloride fluorides. The

following compounds were prepared by precipitation between solutions of tin(II) fluoride and barium chloride: BaSn2F6

(already known, new methods of preparation), BaSn2Cl2F4 (new), BaSnClF3.0.8H2O (new), and a very complex doubly

disordered Ba1-xSnxCl1+xF1-x solid solution (new). The same solid solution, with different properties and a much wider non-

stoichiometry, was obtained by high temperature reactions between SnF2, BaF2 and BaCl2. In the course of the preparation

of the chloride fluorides, it was found that BaSn2F6 and BaSnF4 could be obtained by leaching the chloride fluorides. X-ray

diffraction 119

Sn Mössbauer results will be presented.

47

P25 Thieno[3,2-b]thiophene-based Building Blocks for the Construction of 2D

Thienoacenes

François Magnan and Jaclyn Brusso*

Department of Chemistry, University of Ottawa, Ottawa, ON, Canada fmagn030@uottawa.ca; jbrusso@uottawa.ca

Molecular electronics offer an enticing alternative to traditional silicon-based semiconductors, owing in large part to their

ease of fabrication and the associated lowered cost of production. Device stability and performance remain, however, major

limitations toward more generalized applications. And while charge mobility generally increases upon extension of the

conjugation, stability toward oxidation will usually decrease upon doing so. Incorporation of heteroatoms, such as sulphur,

in the polycyclic framework has been shown to be a viable strategy to address both of these issues. Concurrently, larger

orbitals on the heteroatoms promote π- π stacking and

efficient molecular overlap in the solid-state, a non-trivial factor

in the performance of semiconductors. To this end, our group

has focused on 2D thienoacenes (1, 2) as a way of

extending the effective conjugation, thus enhancing the

optoelectronic properties of the molecules. This

presentation will focus on current efforts toward the

integration of fused thiophenes systems as further ways of

fine tuning the molecular properties.

P26 Friedel-Crafts Reactivity of a Highly Lewis Acidic Phosphonium Catalyst

Towards Benzyl Alcohols and Benzyl Ethers

James H. W. LaFortune, Jiantao Zhu, and Douglas W. Stephan*

Department of Chemistry, University of Toronto, Toronto, ON, Canada james.lafortune@mail.utoronto.ca; dstephan@chem.utoronto.ca

The Fridel-Crafts reaction, wherein a Lewis or Brønsted acid catalyzes carbon-carbon bond formation, endures as the

preferred method of arene and heteroarene alkylation in many industries since its discovery in 1887. Over the past several

decades, significant efforts have been made to lower catalyst loadings and expand the substrate scope. While catalytic

Fridel-Crafts alkylations with benzylic alcohols are well known, alkylations with benzylic ethers are less common.

Furthermore, these reactions generally require high catalyst loadings of 5 to 10 mol%.1 Recently, we have developed a new

class of Lewis acids based on highly electrophilic phosphonium cations. These species have been shown to be highly

reactive, facilitating these reactions with low catalyst loadings.2 In this poster we explore the reaction of these Lewis acids

towards Friedel-Crafts alkylations with benzylic alcohols and ethers.

1 Reuping, M.; Nachtsheim, B. J.; Beilstein Journal of Organic Chemistry, 2010, 6, 6, doi:10.3762/bjoc.6.6.

2 Caputo, C. B.; Hounjet, L. J.; Dobrovetsky, R.; Stephan, D. W.; Science. 2013, 341, 1374. Pérez, M.; Hounjet, L. J.;

Caputo, C. B.; Dobrovetsky, R.; Stephan, D. W.; J. Am. Chem. Soc. 2013, 135, 18308.

48

P27 Stereochemical Reactivity of the Schiff Base Ligand

N-salicylidene-2-aminocyclohexanol in Lanthanide Chemistry

Eleni C. Mazarakioti,1 Katye M. Poole,

2 Luís Cunha-Silva,

3 George Christou,

2 and Theocharis C. Stamatatos

*1

1Department of Chemistry, Brock University, St. Catharines, ON, Canada;

2Department of Chemistry,

University of Florida, Gainesville, Florida, USA; 3REQUIMTE & Department of Chemistry and

Biochemistry, Faculty of Sciences, University of Porto, Porto, Portugal em12xb@brocku.ca; tstamatatos@brocku.ca

The employment of the cis-/trans-mixture of the Schiff base ligand

N-salicylidene-2-aminocyclohexanol, as well as its pure trans-

analogue, in lanthanide cluster chemistry has afforded complexes

with different nuclearities (Figure), indicating the stereochemical

effect of the ligand in the structural identity of polynuclear

compounds. Magnetic and optical studies revealed single-molecule

magnetism and photoluminescence behaviors for all the reported

compounds.1 The organic precursors of this work can be considered

as promising ligands for the construction of dual-acting molecular

species with potential applications in the field of molecule-based

electronics.

1 E. C. Mazarakioti, K. M. Poole, L. Cunha-Silva, G. Christou, Th.

C. Stamatatos, Dalton Trans., 2014, 43, 11456.

P28 Using the difference of Recoilless Fraction for Analytical Purposes

G. Dénès1, *

, A. Muntasar1 , T.N. Mouas

2, S. Boufas

2 and H. Merazig

2

1Laboratory of Solid State Chemistry and Mössbauer spectroscopy, Department of Chemistry and

Biochemistry, Concordia University, Montreal, QC, Canada; 2Laboratoire de Chimie Moléculaire, du

Contrôle de l'Environnement et de Mesures Physico-Chimiques, Département de Chimie, Faculté des Sciences, Université des frères Mentouri de Constantine, Constantine, Algeria, madenes@videotron.ca;

The study of corrosion and surface oxidation of materials, and the protection mechanism, is a highly active area. Tin(II)

spectra can be used to contribute to this field. The energy of the 3/2 →1/2 γ-ray transition of 119

Sn (23.8 keV) being

significantly lower than that of 57

Fe (14.4 keV), the recoil-free fraction of tin compounds is lower than those of iron, at

equal lattice strength and at the same temperature. This gives weaker spectra, sometimes not detectable at ambient

conditions for weak lattices, such as SnCl2.2H2O, while they are easily detected at low temperatures when thermal

vibrations are frozen. In contrast, strong lattice rutile type SnO2 has a very high recoil-free fraction and is easily detected at

room temperature, and the intensity of its line gains little from cooling. We have used the large recoil-free fraction of SnO2

to detect minor amounts of oxidation located in a very thin layer at the surface of particles of tin(II) compounds. We have

also used this method for probing the softness of Sn2+

stannous ion sites in comparison with more rigid Sn(II) covalently

bonded to fluorine, the two sites being randomly distributed in the doubly disordered Ba1-xSnxCl1+yF1-y solid solution. The

large sensitivy of the recoil-free fraction to temperature changes also makes the tin-119 nuclide appropriate for the study of

lattice strength anisotropy (Goldanskii-Karyagin effect).

Figure. The structure of one of the Ln8

clusters discussed in the present work.

49

P29 Decomposition of Phosphine-Functionalized Metathesis Catalysts by Lewis

Donors: Generality and Implications

William L. McClennan, Justin A. M. Lummis, and Deryn E. Fogg*

Department of Chemistry, University of Ottawa, Ottawa, ON, Canada bmccl098@uottawa.ca; deryn.fogg@uottawa.ca

Olefin metathesis is a powerful tool for the assembly of carbon-carbon double bonds. With industrial processes beginning to

emerge for the molecular metathesis catalysts, improved understanding of their decomposition pathways is becoming

increasingly important. We recently described “donor-induced decomposition” of the first-generation Grubbs catalyst

RuCl2(PCy3)2CHPh GI.2 Rapid degradation in the presence of pyridine occurred via a key σ-alkyl species which was

intercepted and characterized by NMR and X-ray analysis.1 Here we provide evidence that the second-generation Grubbs

methlyidene resting states GIIm follow a closely related pathway that is much faster than degradation of complexes in the

absence of pyridine. We also demonstrate that this pathway is general for Lewis donors with widely ranging basicity and

show the impact of this pathway during catalysis with various phosphine-functionalized Grubbs type catalysts. These

findings have important implications for the productivity of Grubbs-class metathesis catalysts.

(1) Lummiss, J. A. M.; McClennan, W. L.; McDonald, R.; Fogg, D. E. Organometallics 2014, 33, 6738-7741.

P30 Main Group Compounds Supported by an NHC Carbene Borate

Tho Nguyen and Georgii I Nikonov*

Department of Chemistry, Brock University, St. Catharines, ON, Canada tho.nguyen@brocku.ca; gnikonov@brocku.ca

N-heterocyclic Carbene (NHC) ligands are ubiquitous in stabilising a variety of transition-metal complexes and find

numberless applications in catalysis. More recently, NHC ligands became popular also in main group chemistry and, in

particular, showed promise in the stabilization of low oxidation state main-group compounds.1-4

In this study, the anionic

NHC/borate ligand [(C6F5)3BCHC{N(2,6-Pri2C6H3)}2C:]

-.Li

+(THF)2 is employed for preparation of a series of main group

element compounds of Si, Ge, B and Zn. Furthermore, the latter can be converted into a Zn-hydride complex which is

being tested in catalytic hydrosilylation and hydroboration.

1. B. Kinjo, B. Donnadieu, M. A. Celik, G. Frenking, G. Bertrand, Science 2011, 333, 610.

2. K. C. Mondal, H. W. Roesky, M. C. Schwarzer, G. Frenking, B. Niepötter, H. Wolf, R. Herbst-Irmer, D. Stalke, Angew.

Chem., Int. Ed. 2013, 52, 2963.

3. Y. Li, K. C. Mondal, H. W. Roesky, H. Zhu, P. Stollberg, R. Herbst-Irmer, D. Stalke, D. M. Anrada, J. Am. Chem. Soc.

2013, 135, 12422.

4. Y. Xiong, S. Yao, S. Inoue, J.D. Epping, M. Driess, Angew. Chem., Int. Ed. 2013, 52, 7147.

50

Figure. Complete structure of the Ni12

wheel compound.

P31 Tandem Catalysis for Water Splitting

Virginie Peneau, Nick Alderman, and Sandro Gambarotta*

Department of Chemistry, University of Ottawa, Ottawa, ON, Canada peneau.virginie@gmail.com; sandro.gambarotta@uottawa.ca

Photocatalytic water splitting is a promising area for the production of hydrogen and oxygen. However, problems arise with

the separation of the mixture of gasses produced, adding large expenses to any commercialised systems. An attractive

proposal is to find a water splitting system involving a shuttle, such that the two gasses are released at separates points in the

cycle, negating the gas separation problem.

This study focuses on the separate production of oxygen and hydrogen from water splitting using tandem catalysis from

carriers that are able to be readily oxidised and reduced.

Two routes are considered; organic and inorganic carriers. Quinone/ benzoquinone is a bio-inspired organic carriers.

Quinone complexes are used by plants to store hydrogen and it has already been shown that quinone can be reduced and

oxidised using various catalyst or electrolysis. Inorganic carriers such as heteropolyacid complexes have shown promising

results using electrolysis. Silicotungstic acid complex was used as hydrogen and electron carrier from water splitting. In a

separate vessel hydrogen was released using platinum catalyst.1

The combination of photoactive species such as TiO2 base catalyst, bismuth, vanadate, and cobalt able to reduce or oxidise

water with to these carriers is investigated.

Water oxidation mediated by a photosensitiser [Ru(bpy)3]2+

persulfate system is a known reaction using persulfate as a

sacrificial electron acceptor. The role of the carriers is to capture hydrogen and electrons. Another investigation is the use of

the previous carriers instead of persulfate with photosensitiser to allow the storage of hydrogen.

P32 Nickel(II) Clusters with Ferromagnetic and Emissive Properties from the Use

of a New Fluorescent Schiff Base Ligand

Panagiota S. Perlepe,1 Luís Cunha-Silva,

2 Kevin Gagnon,

3 Simon J. Teat,

3 Albert Escuer,

4 and Theocharis C.

Stamatatos*1

1Department of Chemistry, Brock University, St. Catharines, ON, Canada,

2REQUIMTE & Department

of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, Porto, Portugal , 3Advanced

Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA, 4Departament de Quimica

Inorganica, Universitat de Barcelona, Barcelona, Spain pp14kk@brocku.ca; tstamatatos@brocku.ca

The choice of the organic chelating/bridging ligand is currently one of the most

appealing chalenges towards the synthesis of new polynuclear 3d-metal complexes

with diverse physical properties, such as magnetism, optics, conductivity and catalysis.

In this work, we present the initial employment of the fluorescent bridging ligand N-

naphthalidene-2-amino-5-chlorobenzoic acid in Ni(II) cluster chemistry.1 Two new

Ni12 and Ni5 clusters with wheel-like and molecular-chain topologies, respectively,

were synthesized; the nature of the ligand has allowed unexpected transformations to

occur, as well as ferromagnetic and emission behaviors to emerge.

[1] P. S. Perlepe, L. Cunha-Silva, K. Gagnon, S. J. Teat, A. Escuer and Th. C.

Stamatatos, submitted to Chem. Eur. J.

51

P33 A New Homogenous Tetradentate Ruthenium-Based Catalyst for the

Hydrodeoxygenation of Biomass-Derived Substrates in Aqueous Acidic Media

Konrad Piaseczny, Ryan Sullivanm and Marcel Schlaf*

Department of Chemistry, University of Guelph, Guelph, ON, Canada kpiasecz@mail.uoguelph.ca; mschlaf@uoguelph.ca

Throughout the past century fossil fuels such as crude oil and natural gas have dominated the production of fuels and

petrochemicals. However, the use of these fossil-derived fuels has well-established negative environmental effects. A shift

to lignocellulosic biomass as a renewable carbon feedstock is therefore desirable, but also challenging as this carbon source

is characterized by an overfunctionalization with highly reactive hydroxyl and other oxygen groups. This problem can

however in principle be overcome through the use of catalytic hydrodeoxygenation reactions that reject oxygen as water.

This project focuses on the evaluation of trans-[Ru(2,9-di-(pyrid-2’-yl)-1,10-phenanthroline)(NCMe)2](OTf)2 as a

homogeneous, hydrogenation catalyst postulated to be stable at the required high temperatures (≥ 175 °C) due to

tetradentate chelation by the highly robust 2,9-di-(pyrid-2’-yl)-1,10-phenanthroline ligand. Complexation (see below) gives

the ruthenium complex, trans-[Ru(2,9-Di-(pyrid-2’-yl)-1,10-phenanthroline)(NCMe)2](OTf)2 in 86 % yield in high purity.

In preliminary test the catalysts realizes the

hydrogenation (175 °C, 800 psi H2, H2O) of 2,5-

hexandione, which forms part of a value chain

from cellulose to hexane, to 2,5-hexandiol and 2,5-

dimethylfuran in > 90 % yield without apparent

decomposition.

P34 Ru(II) and Ru(III)-Anastrozole Anticancer Drug Candidates

Golara Golbaghi, Mohammadmehdi Haghdoost, and Annie Castonguay*

INRS-Institut Armand-Frappier, Laval, Quebec, Canada Golara.Golbaghi@iaf.inrs.ca; Annie.Castonguay@iaf.inrs.ca

Ruthenium complexes receiving increasing attention since antitumor agents NAMI-A and KP1019 successfully entered

phase II clinical trials. In comparison to various platinum compounds that are commonly used for cancer therapy, ruthenium

drug candidates are known to display a higher selectivity towards cancer cells, and to act via different modes of actions,

leading to fewer side effects and preventing the emergence of cancer cell resistance.

By combining cancer cell killing agents (ex: ruthenium) and cancer cell growth inhibitors (ex: Anastrozole), our research

aims at the discovery of superior anticancer therapeutics able to overcome the numerous problems associated with existing

chemotherapies. In this presentation, we will report the synthesis and the characterization of a variety of Ru(II) and Ru(III)-

Anastrozole complexes, as well as our preliminary results regarding their activity against human breast cancer cells.

52

P35 Toward the Development of New Energetic Ionic

Liquids as Green Hypergolic Fuels

Amélie Pialat,a Anguang Hu,

b and Muralee Murugesu*

,a

aDepartment of Chemistry, University of Ottawa, Ottawa, ON,

Canada; bDefense R&D Canada-Suffield Research Centre,

Medicine Hat, AB, Canada apialat@uottawa.ca; m.murugesu@uottawa.ca

Rocket propulsion is due to the spontaneous ignition of hypergolic fuels

upon contact with oxidants inside a combustion chamber.1 This reaction

generates important volumes of hot gases creating thrust. Current

propellant systems mainly use hydrazine and its methylated derivatives as

hypergolic fuels however, they are highly volatile and carcinogenic. For

this reason, during the last decade, the unique properties of ionic liquids;

low vapour pressure, high thermal stability, low flammability and high

designability have considerably drawn attention in the research for new

green hypergolic fuels.2

In this poster, the design, synthesis and study of

the energetic properties of a new family of cyanoborohydride-based ionic

liquids will be presented.

[1] : Holtzmann, R. T. Chemical Rockets 1969, Marcel Dekker, New York.

[2] : Zhang, Q.; Shreeve, J. M. Chem. Rev. 2014, 114, 10527-10574.

P36 Metal Adamantyls; Synthesis and Reactivity

Kamalpreet Singh, Fioralba Taullaj, David Armstrong, and Ulrich W. Fekl*

Department of Chemistry, University of Toronto Mississauga, Mississauga, ON, Canada kamalpreet.singh@mail.utoronto.ca; ulrich.fekl@mail.utoronto.ca

Since its discovery in 1933, adamantane has been at the forefront of

research in cage compounds.1,2

The diamondoid structure of

adamantane gives it unique properties for use in pharmaceuticals,

advanced materials, and catalysis. This versatility led to rigorous

investigation of the compound’s reactivity. The majority of the

chemical transformations affecting adamantane have been limited to

oxidations and halogenations, and very limited progress has been made

in the synthesis of higher diamondoids.2,3

Our research aims to expand the

scope of potential adamantane reactivity by developing novel metal based

adamantyl complexes and exploring the subsequent reactivity of such

compounds. The synthesis and reactivities of a number of new

organometallic adamantyl complexes will be discussed.

1 Fort, R. C.; Schleyer, P. von R. Adamantane: Consequences of the Diamondoid Structure. Chem. Rev. 1964, 64 (3), 277.

2 V V Sevost’yanova and Mikhail M Krayushkin and A G Yurchenko. Advances in the Chemistry of Adamantane. Russian

Chemical Reviews 1970, 39 (10), 817. 3 Schwertfeger, H.; Fokin, A. A.; Schreiner, P. R. Angew. Chem. Int. Ed. 2008, 47, 1022-1036.

53

P37 A Homogeneous Ruthenium Catalyst Based on a Tetradentate Pyridine-Aniline

Ligand for the Hydrodeoxygenation of Biomass Derived Substrates to Value-

Added Chemicals in Aqueous Acidic Media

Maryanne Stones, Konrad Piaseczny, Ryan Sullivan, and Marcel Schlaf*

Department of Chemistry, University of Guelph, Guelph, ON, Canada mstones@mail.uoguelph.ca; mschlaf@uoguelph.ca

The catalytic hydrodeoxygenation of biomass can in

principle provide renewable carbon feedstocks that

can replace or reduce the use of fossil carbon

sources in industrial applications. However, the

development of catalysts that are stable in

aqueous acidic media and at high temperatures, and

exhibit promiscuous catalytic activity towards the

hydrodeoxygenation of biomass derived

substrates is a currently unresolved challenge. This

project focusses on the synthesis of a homogeneous catalyst based on a tetradentate nitrogen-donor ligand containing a rigid

benzene backbone and pendant pyridine groups. Following literature procedures, the ligand N,N'-Bis-(2-pyridylmethyl)-o-

phenylenediamine was synthesized in 40 % yield. A ruthenium complex intermediate [Ru(N,N'-Bis-(2-pyridylmethyl)-o-

phenylenediamine)(Cl)-(DMSO)](Cl) was prepared in 95 % yield. Metathesizing chloride for labile aceto- or benzo-nitrile

ligands with AgOTf at elevated temperatures, two potential catalysts were synthesized from this intermediate. Preparative

scale up of [Ru(N,N'-Bis-(2-pyridylmethyl)-o-phenylenediamine)(NCMe)2](OTf)2 required high-pressure and proved

difficult. The preparation of the alternative complex [Ru(N,N'-Bis-(2-pyridylmethyl)-o-phenylenediamine)(NCPh)2](OTf)2

at ambient pressure allowed structural characterization by mass spectrometry and NMR spectroscopy, but again preparation

on an experimentally and practically viable scale, as well as purification, is pending optimization of the preparative

protocol.

P38 Reactivity of Aryloxo Vanadium(III) and (IV) with Carbon Dioxide

Camilo Viasus, Nick Alderman, and Sandro Gambarotta*

Department of Chemistry, University of Ottawa, Ottawa, ON, Canada cviasusp@uottawa.ca; sandro.gambarotta@uottawa.ca

Activation of small molecules like carbon dioxide by metal complexes is a great challenge due to the high thermodynamic

stability of CO2. If metal complexes are capable to afford deoxygenation or disproportionation, these transformations may

be attractive and useful as long as the process is catalytic. When a M-O function is formed as a by-product instead, the

reaction can be only stoichiometric. Nevertheless, when the transfer is limited to one electron, radical behavior might be

triggered. In this work we are modulating the one or two electron transfer using vanadium(III) and (IV) compounds. We

will present the possibility to switch from deoxygenation to radical behavior to form organic esters.

54

P39 Alkynyl-Based Fluorophosphonium Lewis Acids

Alexander Waked and Douglas W. Stephan*

Department of Chemistry, University of Toronto, Toronto, ON, Canada alexander.waked@mail.utoronto.ca; dstephan@chem.utoronto.ca

Many industrial and pharmaceutical processes, such as hydrogenation and hydrosilylation, are catalyzed by transition metal-

based systems. While these catalysts efficiently mediate these reactions, the dependence on precious metals, environmental

impact, and high cost have led to increased interest in developing metal-free alternatives. Previous research in the Stephan

group has shown that fluorophosphonium cations act as bulky Lewis acids and can catalyze hydrosilylation and

hydrodefluorination reactions.1,2

The current study presents the synthesis of various alkynyl fluorophosphonium systems.

These species provide interesting avenues to the modification of the Lewis acidity at phosphorus and thus offer unique

approaches to new catalytic activity of fluorophosphonium compounds.

1. Caputo, C. B.; Hounjet, L. J.; Dobrovetsky, R.; Stephan, D. W., Science (Washington, DC, U. S.) 2013, 341 (6152), 1374-

1377.

2. Holthausen, M. H.; Mehta, M.; Stephan, D. W., Angew. Chem., Int. Ed. 2014, 53 (25), 6538-6541.

P40 Enantiomerically Pure Bidentate Amine Tethered N-heterocyclic Carbenes:

Synthesis, Transition Metal Complexes and their Asymmetric Catalytic

Applications

Kai Y. Wan, Alan J. Lough, Heiko Rebmann, and Robert H. Morris*

Department of Chemistry, University of Toronto, Toronto, ON, Canada kwan@chem.utoronto.ca; rmorris@chem.utoronto.ca

Certain precious metal complexes are efficient catalysts for the asymmetric hydrogenation (AH) of ketones and imines into

their corresponding enantiopure alcohols and amines, respectively. These products have wide industrial applications,

especially in the pharmaceutical industry. The AH catalysts, however, contain toxic and expensive metals and potentially

harmful and air-sensitive phosphorus ligands. As a consequence, the development of effective catalysts based on benign,

abundant metals such as iron1 and ligands based on organic compounds, such as NHC would provide a significantly greener

approach for AH.2,3

In this presentation, we will discuss our recent development of new chiral NHC ligands that bear

primary amine donors starting from chiral aminoalcohol precursors. This class is highly flexible due to handy electronic

modification at the NHC component and steric modification on the backbone and NHC substituents. Moreover, the amine

moiety can contain a third donor substituent that results in a highly rigid pincer-type ligand structure. During the talk, we

will focus on the coordination chemistry of this class of ligand on transition metals, especially iron. The second part of the

talk will be on the potential applications of this ligand in asymmetric hydrogenation.

1. Lagaditis P., Sues P., Sonnenberg J., Wan K., Lough A., Morris R., J. Am. Chem. Soc., 2014, 136, 1367–1380

2. O, W. W. N.; Lough, A. J.; Morris, R. H. Chem. Commun. 2010, 46, 8240.

3. O, W. W. N.; Morris, R. H. ACS Catal. 2012, 3, 32.

55

P41 Magnetic Circular Dichroism Studies of Iron-bound Human Calprotectin

Tessa M. Woodruff, Toshiki G. Nakashige, Elizabeth M. Nolan, and Michael L. Neidig*

Department of Chemistry, University of Rochester, Rochester, NY, USA twoodru2@ur.rochester.edu; neidig@chem.rochester.edu

Calprotectin (CP) is a metal-sequestering protein found in large

quantities at sites of infection. It is believed that CP prevents

microbial infections by withholding the metal ions needed for

microbial replication and colonization. It has been shown that human CP

binds manganese, iron and zinc. From other studies, it has been

shown that CP also binds iron at its His4/His6 site, an unusual metal

binding site. Here, near-infrared magnetic circular dichroism (MCD)

studies are presented, which permit the evaluation of the coordination

number and geometry of iron(II)-bound CP and its comparison to well

studied iron(II) metalloenzymes containing the common 2-His-1-

carboxylate facial triad iron-binding site. Both first coordination

sphere and distal site mutants are evaluated in order to further probe iron

binding in CP to confirm that iron(II) is bound in a distorted-

octahedral geometry at the His4/His6 site.

P42 Synthesis and Properties of BN-Heterocycles

Dengtao Yang and Suning Wang*

Department of Chemistry, Queen’s University, Kingston, ON, Canada yang.dengtao@queensu.ca; suning.wang@chem.queensu.ca

Among π-conjugated organoboron compounds, BN imbedded aromatic molecules have attracted much research interest and

efforts.1The replacement of a C-C unit in an aromatic molecule with an isoelectronic B-N unit could lead to distinct changes

in its electronic, photophysical, and chemical properties. However, the syntheses of BN substituted polycyclic aromatic

hydrocarbons are in general very challenging.

In 2013, our group reported a photoelimination reaction involving BN-heterocycles.2 The elimination products are highly

luminescent and can be used as emitters in optoelectronic devices. Very recently we further investigated the elimination of

these kinds of BN-heterocycles via thermal pathways3 as well as in electroluminescent (EL) devices

4.

(1) Campbell, P. G.; Marwitz, A. J. V.; Liu, S.-Y. Angew. Chem. Int. Ed.2012, 51, 6074.

(2) Lu, J. S.; Ko, S. B.; Walters, N. R.; Kang, Y.; Sauriol, F.; Wang, S. Angew. Chem. Int. Ed.2013, 52, 4544.

(3) Yang, D.-T.; Mellerup, S. K.; Wang, X.; Lu, J.-S.; Wang, S. Angew. Chem. Int. Ed.2015,54, 5498.

(4) Wang, S.; Yang, D.-T.; Lu, J.; Shimogawa, H.; Gong, S.; Wang, X.; Mellerup, S. K.; Wakamiya, A.; Chang, Y.-L.;

Yang, C.; Lu,Z.-H. Angew. Chem. Int. Ed.2015,DOI : 10.1002/anie.201507770.

0.0

0.4

0.8

1.2

1.6

2.0

De

(M-1

cm

-1)

CP-Ser/Fe(II)

0.0

0.4

0.8

1.2

1.6

2.0

6 8 10 12 14 16

De

(M-1

cm

-1)

Energy (103 cm

-1)

DHis3Asp-CP/Fe(II)

Magnetic Circular Dichroism

56

P43 Converting Amines and Alcohols into Amides or Imines

Matthew Yosurack and Dmitry G. Gusev*

Department of Chemistry, Wilfrid Laurier University, Waterloo, ON, Canada yosu5150@mylaurier.ca; dgoussev@wlu.ca

PNP and NNP osmium complexes from our laboratory[1,2]

catalize dehydrogenative coupling of alcohols and amines to

give imine and amide products, respectively, at 25 – 80 °C,

while using 0.05 – 0.2 mol% [Os].

[1] Bertoli, M.; Choualeb, A.; Lough, A. J.; Moore, B.;

Denis Spasyuk, D.; Gusev, D. G. Organometallics

2011, 30, 3479-3482.

[2] Spasyuk, D.; Vicent, C.; Gusev D. G. J. Am. Chem. Soc.

2015, 137, 3743-3746.

P44 Bone as a Target for Tungsten-Induced Toxicities: Answering Chemical Questions

about Tungsten Deposition in Bone to Elucidate Toxicological Mechanisms

Cassidy VanderSchee and Scott Bohle*

Department of Chemistry, McGill University, Montreal, QC, Canada cassidy.vanderschee@mail.mcgill.ca; scott.bohle@mcgill.ca

Though tungsten is increasingly used in industrial, commercial and medical applications, very little is known regarding its

toxicity at high concentrations largely due to a persisting and unfounded belief in this metal’s inert nature. This gap in

knowledge has recently been highlighted by several cases where high level exposure to tungsten was correlated to severe

medical issues such as leukemia, stroke and seizures. Tungsten has been shown to accumulate in bone with preliminary

studies suggesting that there may be detrimental effects on both bone structure and the immune cells produced in bone

marrow. Through a combination of X-ray Absorption Spectroscopy (XAS) techniques and the use of novel fluorescent

tungsten chelators, we intend to determine tungsten localization and speciation within bone tissue. Establishing the nature

of tungsten in bone will reveal how tungsten deposition affects bone’s structural integrity and gives rise to observed

toxicity.

Figure. Dehydrogenative coupling of primary

alcohols and amines.

57

P45 Water-soluble Platform for Selective Fe(II), Fe(III), Ru(III) and Zn(II) Detection

Nadia O. Laschuk and Olena V. Zenkina*

Faculty of Science, University of Ontario Institute of Technology, Oshawa, ON, Canada Olena.Zenkina@uoit.ca

Transition metals play a vital role in biology and chemistry. Being the most abundant essential trace element in the

human body, iron participates in crucial physiological processes such as oxygen transport, electron transfer, and

enzymatic catalysis. Zinc is the second most abundant transition metal in human body after iron. Unlike iron,

which is required for certain specific functions, zinc is required for general metabolism. However, increased

dietary iron and zinc may cause Alzheimer’s disease, and is linked to development of cancer.1 Even though

ruthenium is not an essential trace element in the human body, it may have significant impact on human health; in

particular, ruthenium complexes were shown to form cross-links with nucleic acids to halt DNA replication.2

Although significant progress has been made in monitoring of Fe(II), Fe(III), Zn(II) and Ru(III) as single-analyte

ions, as well as in detection of Fe(II)-Fe(III) pair, recent research efforts have been focused on the development of

assays that allow simultaneous multi-analyte detection, which is especially important in environmental testings,

food chemistry and molecular biology.3

We report on development of a thoroughly water soluble platform for rapid and sensitive (ppb to ppm level)

detection of Fe2+

, Fe3+

, Ru3+

, and Zn2+

in multicomponent aqueous solutions. Upon reaction with abovementioned

metal ions, it produces a non-distractive Uv-vis and fluorescence readouts that can be analyzed and interpreted

using logic gates concept. Use of the platform do not require preliminary sample treatment, resulting in successful

metal ions discrimination in situ and thus can be potentially applicable for analysis of environmental, food,

biological and biomedical aqueous systems.

1. (a) C. P. Wen, et al Cancer Res., 2014, 74, 6589-6597; (b) L. C. Costello and R. B. Franklin, Mol. Cancer, 2006,

5, 17.

2. A. Bergamo, et al. J. Inorg. Biochem., 2012, 106, 90-99

3. Z. Zhang, D.S. Kim, C.-Y. Lin, H. Zhang, A.D. Lammer, V. M. Lynch,I. Popov, O. Š.Miljanić, E. V. Anslyn, J. L.

Sessler, J. Am. Chem. Soc. 2015, 137, 7769-7774.

P46 An Organo-Thulium Family of Single-Ion Magnets: Is Symmetry Enough?

Katie L. M. Harriman, Ilia Korobkov, and Muralee Murugesu*

Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, ON, Canada kharr093@uottawa.ca; m.murugesu@uottawa.ca

Single-molecule magnets (SMMs) exhibit slow relaxation of the magnetization of purely molecular origin, making them

excellent candidates for electronics-based applications; specifically in high-density information storage, molecular

spintronics, and quantum computing. However, implementation of these types of materials into practical devices will rely

heavily on increasing their energy barrier to spin reversal (Ueff). Throughout the last decade, growing research efforts have

been directed towards the synthesis of single-ion magnets (SIMs) with the goal of maximizing Ueff through tailoring single-

ion anisotropy. The 4f-elements represent excellent candidates for SIMs due to their large intrinsic magnetic anisotropy,

however, they are often plagued with significant ground state quantum tunneling of the magnetization (QTM), which

drastically reduces Ueff.. This problem becomes even more difficult to overcome in non-Kramers ions, (integer spin systems)

where ground state QTM is not formally forbidden as it is with Kramers ions (non-integer spin systems). One of the ways to

circumvent this problem is to design systems which exhibit very high symmetry. As such, we have turned our attention

towards organometallic compounds; where we have synthesized a family of cyclooctatetraenide (COT2-

) complexes with

thulium, a non-Kramers ion (S = 1). Thulium remains one of the most rarely studied lanthanide ions, both in terms of its

chemistry and its slow relaxation properties. This presentation will outline the synthetic route, and the subsequent

challenges faced in designing a family of organo-thulium complexes, as well as their SIM properties investigated through

SQUID magnetometry.

58

P47 Arsenic Speciation in Mushrooms Subject to Thermal Treatments

Jessica Henry, Iris Koch,* Jennifer Scott,

* and Kenneth J. Reimer

*

Department of Chemistry and Chemical Engineering, Royal Military College of Canada, Kingston, ON, Canada jessica.henry@rmc.ca; koch-i@rmc.ca; jennifer.scott@rmc.ca; reimer-k@rmc.ca

Arsenic is an element found in the environment in many different chemical forms (referred to as species), each having

unique chemical, physical and biological properties. The different species range in their toxicities, with among the most

toxic arsenic species including inorganic forms, such as arsenite (As(III)) and arsenate (As(V)). Generally, pentavalent

organoarsenic compounds are less toxic and aresenobetaine (AB) is the only species considered non-toxic. Where there are

no natural or anthropogenic sources of arsenic contamination, food is the main source of intake for this metalloid. Higher

levels of arsenic are generally found in foods such as seafood, rice, and sometimes mushroom. AB is the principal arsenic

form in seafood and many mushrooms species. Preparations of food, such as cooking treatments, have been found to alter

the arsenic speciation in seafood such as the degradation of AB to dimethylarsinic acid (DMA), and tetramethylarsonium

ion (TETRA), as well as less prevalent amounts of arsenocholine (AC) and monomethylarsonic acid (MMA). In this study,

four edible mushroom species (Lactarius deliciosus, Leccinum scabrum, Boletus edulis and Calvatia gigantea) were

collected and treated to simulate cooking scenarios (barbequed and fried). The samples were analyzed for total arsenic using

ICP-MS and for arsenic species using HPLC-ICP-MS. A consistent decrease in the total arsenic concentration was seen in

all of the cooked samples, in comparison to their raw (untreated) concentrations. AB was found to be transformed to more

toxic forms in both the fried and barbequed samples for the Calvatia sp.. Therefore, it may be necessary to consider the

effect of thermal treatments on arsenical species when determining risk associated with mushroom intake.

P48 Benzimidazolium Bicarbonates as Air-stable Precursors of N-Heterocyclic

Carbenes (NHCs): Novel Synthetic Routes and Applications to Gold Surfaces

Mina R. Narouz, Christene A. Smith, Cathleen M. Crudden,* and J. Hugh Horton

*

Department of Chemistry, Queen’s University, Kingston, ON, Canada 13mn23@queensu.ca; cruddenc@chem.queensu.ca; hugh.horton@chem.queensu.ca Recent results from the Crudden and Horton laboratories demonstrated the formation of ultrastable self-assembled

monolayers (SAMs) of N-heterocyclic carbenes (NHC) on gold surfaces where NHCs were generated in a glove box

using a strong base.1 Although Fevre et al. showed that imidazol(in)ium bicarbonates could behave as an air stable source

of NHCs, their procedures for the preparation of imidazolium bicarbonates via anion-metathesis using KHCO3 resulted in

highly variable levels of exchange.2 In our current work, novel synthetic routes were developed to prepare pure, air-stable

benzimidazolium bicarbonates ([NHC(H)][HCO3] ) from the iodide counterparts. For the first time, these bench-stable

bicarbonates were shown to effectively form NHC-based SAMs on gold surfaces in methanol at room temperature

without the need for water and oxygen-free conditions.

1Crudden C.

M. et al., Nature Chem., 2014, 6, 409-414. 2Fèvre M. et al., J. Am.Chem. Soc., 2012, 134, 6776–6784.

59

P49 Picolyl-NHC Metal Complexes: Syntheses and Reactivities

Qiuming Liang, Trevor Janes and Datong Song*

Department of Chemistry, University of Toronto, Toronto, ON, Canada walter.liang@mail.utoronto.ca; dsong@chem.utoronto.ca

The chemistry of metal-ligand cooperation is useful in many bond activation processes. Milstein has demonstrated a mode

of H-Y (Y = H, OH, OR, NH2, NR2, C) bond activation via aromatization-dearomatization processes in pyridine- or

acridine- based tridentate (PNN or PNP) pincers1. This system is successfully used as catalysts in many environmentally

benign transformations with different metal centers1. Our group has studied similar pincer on ruthenium by substituting the

phosphours arm by NHC2. We are then interested in related bidentate cooperative ligands on earth abundant metals (ie. Iron,

cobalt, nickel). Picolyl-NHC type ligands are chosen to study as it contains pyridyl methylene which should be accessible

towards aromatization- dearomatization and further bond activations (Scheme 1.). By coordination to iron and

deptrotonation, low coordinate iron chemistry can also be explored. This poster illustrates picolyl-NHC iron(II) complexes

syntheses. Preliminary results of reactivities and deprotonation study are also presented.

Scheme 1. Proposed aromatization-dearomatization on picolyl-NHC iron system.

1. D. Milstein et al., Acc. Chem. Commun. 2011, 588

2. D. Song et al., Chem. Commun. 2011, 8349

60

Participants

ACS International – CAS Pine Research Instrumentation Université de Montréal University of Rochester Dr. Mostafa Hatam Dr. Li Sun Prof. Frank Schaper Prof. Michael Neidig

Prof. Davit Zargarian Stephanie Carpenter

Air Liquide Canada Inc. Queen’s University Thomas Auvray Tessa Woodruff Ross Stirling Prof. Cathleen Crudden Suéli Bonafim

Matt Coleman Dr. Matthew Zamora Pargol Daneshmand University of Toronto

Dr. Patrick Eisenberger Antoine Douchez Prof. Robert Morris

Brock University Mohammed Affan Valérie Hardouin Duparc Prof. Ulrich Fekl

Prof. Georgii Nikonov Zach Ariki Maryam Abdinejad

Prof. Theocharis Stamatatos Edward Cieplechowicz University of Guelph Julia Bayne Prof. Melanie Pilkington Joshua Clarke Prof. Marcel Schlaf Karl Demmans

Prof. Costa Metallinos Ramjee Kandel Elnaz Latifi Louie Fan Iryna Alshakova Shuang Liang Konrad Piaseczny Trevor Janes

Tho Nguyen Sean McDonald Maryanne Stones James LaFortune

Dimitrios Alexandropoulos Colleen McIlwain Jolie Lam Panagiota Perlepe Jennifer McLeod University of Ontario Institute of

Technology

Kamalpreet Singh

Alysha Alaimo Soren Mellerup Samantha Smith

Eleni Mazarakioti Mina Narouz Prof. Olena Zenkina Fioralba Taullaj Paul Richardson Sarah Piotrkowski Alexander Waked

Dimosthenis Giannopoulos Jason Rygus University of Ottawa Kai Wan

Marnie Edwardson Dengtao Yang Prof. Muralee Murugesu Pavel Zatsepin Majeda Al Hareri Prof. Jaclyn Brusso

Rigaku Oxford Diffraction Prof. Tom Baker University of Toronto Scarborough

Bruker Dr. Lee Daniels Prof. Deryn Fogg Dr. Zhe She Dr. Dan Frankel Dr. Jamie Frost Dr. Iraklii

Cary Bauer Royal Military College of Canada Dr. Cassandra Hayes Annaleizle Ferranco

Joseph Weiss Prof. Ken J. Reimer Nicholas Alderman Prof. Gord Simons Gwendolyn Bailey University of Windsor

Concordia University Prof. Danny Pagé Adrian Botti Prof. Jeremy Rawson

Prof. Xavier Ottenwaelder Prof. Jennifer Scott Alex Daniels Justin Binder Prof. Georges Denes Capt. Ross Franklin Emily Gee Mohamad Harb

Dr. Abdualhafed Muntasar Capt. Nicholas Beaudry Katie Harriman Erika Haskings

Laura Andrea Rodriguez Solano Capt. Matt McTaggart Andrew Hollingshead Mitchell Nascimento Capt. Craig Williams Rebecca Holmberg

INRS - Université du Québec Vishva Shah Elizabeth Kleisath Western University

Prof. Annie Castonguay Jessica Henry Thomas Lacelle Prof. Johanna Blacquiere Dr. Medhi Haghdoost Sojung Lee Dr. Patrick Crewdson

Anissa Brahami Ryerson University Maykon Lemes Ryan Maar

Golara Golbaghi Prof. Daniel Foucher François Magnan Samantha Novoa Amal Thamri Dr. Aman Khan William McClennan

Jasveer Dhindsa Virginie Peneau Wilfred Laurier University

McGill University Jennifer Huynh Stephanie Rufh Prof. Dmitri Goussev Dr. Kristopher Rasadiuk Julie Loungxay Ryan Sullivan Prof. Oleg Shirobokov

Dr. Munendra Yadav Jeffrey Pau Camilo Viasus Matthew Yosurack

Cassidy Vanderschee Muhammad Yousaf Nathan Yutronkie Yixin Zhang York University

McMaster University Systems for Research Prof. Barry Lever

Prof. David Emslie Jerry Windsor-Martin University of Pennsylvania Prof. Lavoie Jeffrey Price Prof. Daniel J. Mindiola Faidh Hana

Université des frères Mentouri de

Constantine, Algeria

Nick Zinck

MEGS Specialty Gases Inc. David de Bellefeuille Prof. Hocine Merazig

61

Conference Chair

Jennifer Scott

Assistant Chair

Capt. Ross Franklin

Organizing Committee

Vishva Shah

Rick Melanson

Capt. Nicholas Beaudry

Website and Finances

Bryan Bailey

Mary Darlington

Special Mention

RMC Club of Canada

Department of Chemistry and Chemical Engineering

Royal Military College of Canada

Thank you to all of our volunteers !!

Matt McTaggart Brandon Kiedyk Capt. Brent Limbeek

Jennifer Snelgrove William Payton-Stewart 2Lt. Rabia Soni

Neda Bavarian Jonathan Saulnier Samantha McDermott

Michelle Nearing Olivier Lebel William Carle

Deborah Durbin Alex Beaulieu Alex Landry

Summer Li Myrian Rochon Capt. Craig Williams

Diana Tyner Victoria Brown Hugo Hazledine

Laura Oligvie Trevor Reid Mitchell Brown

Shuang Liang Andrew Juvonen Michael Cherry

Anbareen Farooq Michael Skipwith Varun Senthilkumar

Jessica Henry Clarize Virtusio Blaire Coffey

Emily Corcoran Jaden Rook Kevin Pathinather

Nicholas Bourgon Tae Kim Morgan Chaffee-Goehr

Zackary Thomson Jacob Tamman Jordon Gjelsvik

Tristan Blaikie Kieran Marks Gregory Garber

Eliot Sulima Gabriel Paquet Cecily McDonnell

Melanie Hughes Ian Marcoux Linda Marois

Kela Weber Paul Chan Kathy Nielsen

Marc Button Pavel Samuleev Tim Nash

Kommy Farahani Daniela Loock John Saunders