Organometallic Chemistry

Volume 40

A Specialist Periodical Report

Organometallic Chemistry

Volume 40

EditorsI. Fairlamb and J. Lynam, University of York, UK

AuthorsMichael R. Chapman, University of Leeds, UKChristopher G. Frost, University of Bath, UKXavier Just-Baringo, University of Manchester, UKBenjamin R. M. Lake, University of Edinburgh, UKPo Man Liu, University of Bath, UKPatricia Marce, University of Bath, UKGerard P. McGlacken, University College Cork, IrelandEoin O Muimhneachain, University College Cork, IrelandNathan J. Patmore, University of Huddersfield, UKAndrew J. Peel, University of Cambridge, UKDavid Procter, University of Manchester, UKJonathan S. Ward, University of York, UKAndrew E. H. Wheatley, University of Cambridge, UKCharlotte E. Willans, University of Leeds, UKIrem Yalavac, University of Manchester, UK

Print ISBN: 978-1-84973-984-9PDF eISBN: 978-1-78262-396-0ISSN: 0301-0074DOI: 10.1039/9781782623960

A catalogue record for this book is available from the British Library

r The Royal Society of Chemistry 2016

All rights reserved

Apart from fair dealing for the purposes of research or private study fornon-commercial purposes, or for private study, criticism or review, aspermitted under the Copyright, Designs and Patents Act, 1988 and theCopyright and Related Rights Regulations 2003, this publication may not bereproduced, stored or transmitted, in any form or by any means, without theprior permission in writing of The Royal Society of Chemistry, or in the caseof reproduction in accordance with the terms of the licences issued by theCopyright Licensing Agency in the UK, or in accordance with the terms of thelicences issued by the appropriate Reproduction Rights Organization outsidethe UK. Enquiries concerning reproduction outside the terms stated hereshould be sent to The Royal Society of Chemistry at the address printed onthis page.

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PrefaceIan J. S. Fairlamb and Jason M. LynamDOI: 10.1039/9781782623960-FP005

To celebrate the 40th volume in the SPR series on organometallicchemistry a number of previous contributors have written articles whichsummarise the state-of-the-art within a number of important themes inmodern organometallic chemistry.

Organometallic chemistry continues to have an important and growingrole in synthetic chemistry, and this is reflected in articles by ChristopherFrost, Patricia Marce and Po Man Liu who examine developments inC–H functionalization reactions; Xavier Just-Baringo, Irem Yalavac andDavid Procter detail progress in the use of SmI2 in synthesis and Eoin OMuimhneachain and Gerard McGlacken discuss the important roleplayed by nanoparticles in palladium catalysed cross-coupling reactions.Many of these applications are supported by fundamental insights intothe structure and bonding of transition metal complexes, with thisin mind Benjamin Lake, Michael Chapman and Charlotte E. Willansdescribe the developing chemistry of N-heterocyclic carbene ligands,whose role has expanded from a simple spectator co-ligand to taking anactive role in a given reaction. Furthermore, Nathan J. Patmore reports onsome recent developments in the chemistry of metal–metal quadruplebonds and Andrew J. Peel and Andrew E. H. Wheatley discuss some of thelatest findings in the organometallic chemistry of the alkali and coinagemetals.

Organometallic complexes have an increasingly important role astherapeutic agents and Jonathan Ward reports on the application ofmetal carbonyl complexes as therapeutic agents.

We believe, therefore, that this volume provides a snap-shot of some ofthe most important developments in modern organometallic chemistry.

Organomet. Chem., 2016, 40, v–v | v

�c The Royal Society of Chemistry 2016

CONTENTS

Cover

The cover image shows theorganopalladium compoundPd2(dba)3. Image by PrecisionGraphic Services.

Preface v

Ian J. S. Fairlamb and Jason M. Lynam

Overcoming synthetic challenges in target synthesis usingSmI2: recent advances

1

Xavier Just-Baringo, Irem Yalavac and David Procter1 Introduction 12 Natural products synthesis 23 Synthesis of non-natural bioactive compounds 234 Organic materials 235 Conclusions 30References 30

Pd(0) nanoparticles (NPs) as catalysts in cross-coupling reactionsand the homogeneous vs. heterogeneous debate

33

Eoin O Muimhneachain and Gerard P. McGlacken1 Introduction 332 Synthesis and stabilisation of nanoparticles 343 ‘Homeopathic palladium’ and nanoparticles as

catalysts35

4 Heterogeneous catalysis vs. homogeneous catalysis 375 Recyclability and reusability 446 More notable examples 45

Organomet. Chem., 2016, 40, vii–ix | vii

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7 Conclusion and outlook 498 Acknowledgements 50References 50

Recent developments in selective C–H functionalisation 54

Christopher G. Frost, Patricia Marce and Po Man Liu1 Introduction 542 C–H activation mechanism 543 Ru(II) catalysed sp2-C–H functionalisation 574 Metal catalysed sp2 meta-functionalisation 75References 82

Recent advances in the chemistry of metal–metalquadruple bonds

88

Nathan J. Patmore1 Introduction 882 Chromium 893 Molybdenum and tungsten 914 Technetium 1005 Rhenium 1026 Summary 103References 104

N-Heterocyclic carbenes; partakers not just spectators 107

Benjamin R. M. Lake, Michael R. Chapman andCharlotte E. Willans

1 Introduction 1072 C–C reductive elimination 1073 C–X reductive elimination 1144 Ring-opening 1205 Migratory insertion 1226 C–C and C–H activation 1267 Miscellaneous 1348 Conclusions and outlook 136References 136

Carbon monoxide-releasing molecules: therapeutic moleculeswith a wide variety of medical applications

140

Jonathan S. Ward1 Introduction 140References 174

viii | Organomet. Chem., 2016, 40, vii–ix

Alkali/coinage metals – organolithium, organocuprate chemistry 177

Andrew J. Peel and Andrew E. H. Wheatley1 The alkali metals 1772 Group 11 metals 181Abbreviations 193References 194

Organomet. Chem., 2016, 40, vii–ix | ix

Abbreviations

Ac acetateacac acetylacetonateacacen N,N0-ethylenebis(acetylacetone iminate)Ad adamantylAIBN azoisobutyronitrileampy 2-amino-6-methylpyridineAr arylAr* 2,4,6-tri(tert-butyl)phenylAr0f 3,5-bis(trifluoromethyl)phenylarphos 1-(diphenylphosphino)-2-(diphenylarsino)ethaneATP adenosine triphosphateAzb azobenzene9-BBN 9-borabicyclo[3.3.1]nonaneBHT 2,6-dibutyl-4-methylphenylBiim biimidazoleBINAP 2,20-bis(diphenylphosphino)-1,10-binaphthylbipy 2,20-bipyridylBis bis(trimethylsilyl)methylbma 2,3-bis(diphenylphosphino)maleic anhydrideBNCT boron neutron capture therapyBp biphenylbpcd 4,5-bis(diphenylphosphino)cyclopent-4-ene-1,3-dionebpk benzophenone ketyl (diphenylketyl)Bpz4 tetra(1-pyrazolyl)borateBut

2bpy 4,40-di-tert-butyl-2,20-bipyridinet-bupy tert-butylpyridineBz benzylBzac benzoylacetonatecbd cyclobutadiene1,5,9-cdt cyclododeca-1,5,9-trienechd cyclohexadienechpt cycloheptatrieneCIDNP chemically induced dynamic nuclear polarisation[Co] cobalamin(Co) cobaloxime [Co(dmg)2 derivative]cod cycloocta-1,5-dienecoe cyclooctenecot cyclooctatrieneCP/MAS cross polarisation/magnetic angle spinningCp Z5-cyclopentadienylCpR Z5-alkylcyclopentadienylCp* Z5-pentamethylcyclopentadienylCp0 trimethylsilylcyclopentadienylCp00 tetramethylethylcyclopentadienylCV cyclic voltammetry(ogram)CVD chemical vapour deposition

x | Organomet. Chem., 2016, 40, x–xiv

�c The Royal Society of Chemistry 2016

Cy cyclohexylCyclam 1,4,8,11-tetraazacyclotetradecaneCym p-cymeneCyttp PhP(CH2CH2CH2PCy2)2

dab 1,4-diazabutadienedabco 1,4-diazabicyclo[2.2.2]octanedba dibenzylideneacetonedbpe 1,2-bis(dibutylphosphino)ethaneDBU 1,8-diazabicyclo[5.4.0]undec-7-eneDCA 9,10-dicyanoanthracenedepe 1,2-bis(diethylphosphino)ethanedepm 1,2-bis(diethylphosphino)methaneDFT density functional theorydiars o-phenylenebis(dimethyl)arsinediarsop {[(2,2-dimethyl-1,3-dioxolan-4,5-diyl)bis(methylene)]-

bis-[diphenylarsine]}dien diethylenetriaminediop {[(2,2-dimethyl-1,3-dioxolan-4,5-diyl)bis(methylene)]-

bis-1-[diphenylphosphine]}DIPAMP 1,2-bis(phenyl-o-anisoylphosphino)ethanediphos 1,2-bis(diphenylphosphino)ethanedipp 2,6-diisopropylphenyldipyam di-(2-pyridyl)amineDMAD dimethyl acetylenedicarboxylateDMAP 2-dimethylaminopyridinedmbpy dimethylbipyridineDME 1,2-dimethoxyethaneDMF N,N-dimethylformamidedmg dimethylglyoximatedmgH monoanion of dimethylglyoximedmgH2 dimethylglyoximeDMP dimethylpiperazinedmpe 1,2-bis(dimethylphosphino)ethanedmpm bis(dimethylphosphino)methanedmpz 1,3-dimethylpyrazolylDMSO dimethyl sulfoxidedpae 1,2-bis(diphenylarsino)ethanedpam bis(diphenylarsino)methanedppa 1,2-bis(diphenylphosphino)ethynedppb 1,4-bis(diphenylphosphino)butanedppbz 1,2-bis(diphenylphosphino)benzenedppe 1,2-bis(diphenylphosphino)ethanedppf 1,10-bis(diphenylphosphino)ferrocenedppm bis(diphenylphosphino)methanedppp 1,3-bis(diphenylphosphino)propaneDSD diamond–square–diamondedt ethane-1,2-dithiolateEDTA ethylenediaminetetraacetateee enantiomeric excess

Organomet. Chem., 2016, 40, x–xiv | xi

EELS electron energy loss spectroscopyEH MO extended Huckel molecular orbitalELF electron localisation functionen ethylene-1,2-diamineES MS electrospray mass spectrometryEXAFS extended X-ray absorption fine structureF6acac hexafluoroacetylacetonateFc ferrocenylFe* Fe(CO)2Cp*Fp Fe(CO)2CpFp0 Fe(CO)2Z

5-(C5H4Me)FTIR Fourier transform infraredFVP flash vacuum pyrolysisglyme ethyleneglycol dimethyl etherGVB generalised valence bondHBpz3 tris(pyrazolyl)borateHBpz*3 tris(3,5-dimethylpyrazolyl)borateH4cyclen tetraaza-1,4,7,10-cyclododecaneHEDTA N-hydroxyethylethylenediaminetetraacetatehfa hexafluoroacetonehfacac hexafluoroacetylacetonatohfb hexafluorobutyneHMPA hexamethyl phosphoric triamideHNCC high nuclearity carbonyl clusterHOMO highest occupied molecular orbitalIGLO individual gauge for localised orbitalsim imidazoleIs* 2,4,6-triisopropylphenylISEELS inner shell electron energy loss spectroscopyKTp potassium hydrotris(1-pyrazolyl)borateLDA lithium diisopropylamideLiDBB lithium di-tert-butylbiphenylLMCT ligand to metal charge transferLNCC low nuclearity carbonyl clusterMAO methyl alumoxaneMe2bpy 4,40-dimethyl-2,20-bypyridylMe6[14]dieneN4 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetra-

deca-4,11-dieneMe6[14]N4 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetra-

decane4,7-Me2phen 4,7-dimethyl-1,10-phenanthroline3,4,7,8-Me4phen 3,4,7,8,-tetramethyl-1,10-phenanthrolineMes mesitylMes* 2,4,6-tributylphenylMeTHF methyltetrahydrofuranmcpba metachloroperbenzoic acidMLCT metal–ligand charge transferMTO methylrhenium trioxidenap 1-naphthyl

xii | Organomet. Chem., 2016, 40, x–xiv

nb norbornenenbd norbornadieneNBS N-bromosuccinimideNCS N-chlorosuccinimideNCT neutron capture theoryNeo neopentylNp 1-naphthylnp3 N(CH2CH2PPh2)3

nta nitrilotriacetateOEP octaethylporphyrinOTf trifluoromethanesulfonate (triflate)OTs p-toluenesulfonate (tosylate)Pc phthalocyaninPES photoelectron spectroscopyPMDT pentamethylenediethylenetetraminepd pentane-2,4-dionatephen 1,10-phenanthrolinepic pyridine-2-carboxylic acidPin (þ)-pinanylPmedta pentamethyldiethylenetriaminepp3 P(CH2CH2PPh2)3

[PPN]þ [(Ph3P)2N]þ

py pyridinepydz pyridazinepz pyrazolylR-PROPHOS (R)-(þ)-1,2-bis(diphenylphosphino)propaneR,R-SKEWPHOS (2R,4R)-bis(diphenylphosphino)pentaneRDF radial distribution functionROMP ring opening metathesis polymerisationsal salicylaldehydesalen N,N0-bis(salicylaldehydo)ethylenediaminesaloph N,N-bisalicylidene-o-phenylenediamineSCF self consistent fieldTCNE tetracyanoethyleneTCNQ 7,7,8,8-tetracyanoquinodimethaneterpy 2,20,200-terpyridyltetraphos 1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecaneTFA trifluoroacetic acidtfbb tetrafluorobenzobarrelenetfacac trifluoroacetylacetonatoTHF tetrahydrofuranthsa thiosalicylate (2-thiobenzoate)tht tetrahydrothiophenTMBD NNN0N00-tetramethyl-2-butene-1,4-diamineTMEDA (tmena) tetramethylethylenediaminetmp 2,2,6-6-tetramethylpiperidinoTMS tetramethylsilanetol tolylTP hydrotris(1-pyrazolyl)borate

Organomet. Chem., 2016, 40, x–xiv | xiii

TP* hydrotris(2,5-dimethylpyrazolyl)borateTPP meso-tetraphenylporphyrinTrip 2,4,6-triisopropylphenylTriph 2,4,6-(triphenyl)phenyltriphos 1,1,1-tris(diphenylphosphinomethyl)ethaneTRIR time resolved infrared (spectroscopy)Tsi tris(trimethylsilyl)methyl (Me3Si)3CTTF tetrathiafulvalenevi vinylWGSR water gas shift reactionXPS X-ray photoelectron spectroscopyXyl xylyl

xiv | Organomet. Chem., 2016, 40, x–xiv