Supporting Information: The Sulfur-Fluorine Gauche Effect ...€¦ · All reactions were performed...

Supporting Information: The Sulfur-Fluorine Gauche Effect in

Coinage Metal Complexes: Augmenting Conformational

Equilibria by Complexation.

Nico Santschi[a,b]*, Christian Thiehoff[a], Mareike C. Holland[a,c], Constantin G. Daniliuc[a,§], K. N.

Houk[c]*, Ryan Gilmour[a,b]*

[a] Institute for Organic Chemistry, Westfälische Wilhelms-Universität Münster, Corrensstrasse 40, Münster,

Germany. [b]

Excellence Cluster EXC 1003, Cells in Motion, Westfälische Wilhelms-Universität, Münster, Germany. [c]

Department of Chemistry and Biochemistry, University of California Los Angeles, 607 Charles E. Young Drive East, Los Angeles 90095-1569, USA.

S1

Content

General Methods ................................................................................................................................... S2

X-Ray Diffraction .................................................................................................................................... S2

Computational Details ........................................................................................................................... S4

NMR Spectra of Complexes 2 & 3 ....................................................................................................... S35

1H NMR (600 MHz) Spectrum of Complex 2 .................................................................................... S35

13C NMR (151 MHz) Spectrum of Complex 2 ................................................................................... S35

19F NMR (564 MHz) Spectrum of Complex 2 ................................................................................... S36

HSQC Spectrum of Complex 2 ......................................................................................................... S36

HMBC Spectrum of Complex 2 ........................................................................................................ S37

Variable Temperature 1H NMR (600 MHz) of Complex 2 ................................................................ S37

1H NMR (600 MHz) Spectrum of Complex 3 .................................................................................... S38

13C NMR (151 MHz) Spectrum of Complex 3 ................................................................................... S38

19F NMR (564 MHz) Spectrum of Complex 3 ................................................................................... S39

Stacked 1H NMR (600 MHz) Spectra of 1a, 3, 2 ............................................................................... S39

S2

General Methods All reactions were performed under an atmosphere of argon in dried glassware, except when using

aqueous reagents. All chemicals were reagent grade and used as supplied unless stated otherwise.

Ligand 1a was prepared as previously reported by our group.[1] Reactions were magnetically stirred

unless stated otherwise. 1H NMR, 13C NMR and 19F NMR spectra were recorded on an Agilent DD2

600 spectrometer. Chemical shifts (δ) are reported in ppm relative to the residual solvent peak. The

multiplicities are reported as: s = singlet, d = doublet, t = triplet, q = quartet, sext = sextet, m =

multiplet, br = broad. Melting points were measured on a Büchi B540 melting point apparatus. IR

spectra were measured on a Perkin-Elmer Spectrum 100 FTIR spectrometer and reported in cm-1. The

intensities of the bands are reported as: w = weak, m = medium, s = strong. High-resolution mass

spectra (HR ESI and EI MS) and elemental analyses were performed by the MS service at the Organic

Chemistry Institute of the WWU Münster.

[1] Thiehoff, C.; Holland, M. C.; Daniliuc, C.; Houk, K. N.; Gilmour, R. Chem. Sci. 2015, 6, 3565-3571.

X-Ray Diffraction Data sets were collected with a D8 Venture Dual Source 100 CMOS diffractometer. Programs used:

data collection: APEX2 V2014.5-0 (Bruker AXS Inc., 2014); cell refinement: SAINT V8.34A (Bruker AXS

Inc., 2013); data reduction: SAINT V8.34A (Bruker AXS Inc., 2013); absorption correction, SADABS

V2014/2 (Bruker AXS Inc., 2014); structure solution SHELXT-2014 (Sheldrick, 2014); structure

refinement SHELXL-2014 (Sheldrick, 2014). R-values are given for observed reflections, and wR2

values are given for all reflections. R-values are given for observed reflections, and wR2 values are

given for all reflections.

X-Ray Crystal Structure Analysis of 2: A colorless needle-like specimen of C51H51Au3Cl3F3S3 2 x

CH2Cl2, approximate dimensions 0.029 mm x 0.065 mm x 0.305 mm, was used for the X-ray

crystallographic analysis. The X-ray intensity data were measured. A total of 1057 frames were

collected. The total exposure time was 13.21 hours. The frames were integrated with the Bruker

SAINT software package using a narrow-frame algorithm. The integration of the data using a

monoclinic unit cell yielded a total of 92891 reflections to a maximum θ angle of 25.35° (0.83 Å

resolution), of which 10066 were independent (average redundancy 9.228, completeness = 99.9%,

Rint = 12.88%, Rsig = 6.18%) and 9031 (89.72%) were greater than 2σ(F2). The final cell constants of a =

8.0568(5) Å, b = 14.4365(8) Å, c = 24.0039(16) Å, β = 99.640(3)°, volume = 2752.5(3) Å3, are based

upon the refinement of the XYZ-centroids of 9805 reflections above 20 σ(I) with 5.128° < 2θ < 52.81°.

Data were corrected for absorption effects using the multi-scan method (SADABS). The ratio of

minimum to maximum apparent transmission was 0.779. The calculated minimum and maximum

transmission coefficients (based on crystal size) are 0.1820 and 0.7910. The final anisotropic full-

matrix least-squares refinement on F2 with 622 variables converged at R1 = 3.92%, for the observed

data and wR2 = 6.78% for all data. The goodness-of-fit was 1.119. The largest peak in the final

difference electron density synthesis was 1.206 e-/Å3 and the largest hole was -1.661 e-/Å3 with an

RMS deviation of 0.198 e-/Å3. On the basis of the final model, the calculated density was 2.032 g/cm3

and F(000), 1608 e-.

X-Ray Crystal Structure Analysis of 3: A colorless prism-like specimen of C34H34Ag2F14S2Sb2,

approximate dimensions 0.132 mm x 0.226 mm x 0.285 mm, was used for the X-ray crystallographic

analysis. The X-ray intensity data were measured. A total of 1279 frames were collected. The total

exposure time was 7.43 hours. The frames were integrated with the Bruker SAINT software package

S3

using a narrow-frame algorithm. The integration of the data using an orthorhombic unit cell yielded a

total of 168450 reflections to a maximum θ angle of 26.37° (0.80 Å resolution), of which 7980 were

independent (average redundancy 21.109, completeness = 99.7%, Rint = 3.91%, Rsig = 1.22%) and 7915

(99.19%) were greater than 2σ(F2). The final cell constants of a = 17.4030(7) Å, b = 14.0758(6) Å, c =

15.9506(6) Å, volume = 3907.3(3) Å3, are based upon the refinement of the XYZ-centroids of 9626

reflections above 20 σ(I) with 5.332° < 2θ < 55.14°. Data were corrected for absorption effects using

the multi-scan method (SADABS). The ratio of minimum to maximum apparent transmission was

0.905. The calculated minimum and maximum transmission coefficients (based on crystal size) are

0.5300 and 0.7290. The final anisotropic full-matrix least-squares refinement on F2 with 487 variables

converged at R1 = 3.02%, for the observed data and wR2 = 7.56% for all data. The goodness-of-fit

was 1.210. The largest peak in the final difference electron density synthesis was 1.556 e-/Å3 and the

largest hole was -0.981 e-/Å3 with an RMS deviation of 0.132 e-/Å3. On the basis of the final model,

the calculated density was 2.094 g/cm3 and F(000), 2368 e-.

[1] Bruker (2013). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.

[2] SHELXT und SHELXL Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

S4

Computational Details Geometry optimizations of minima were carried out in the gas phase using Gaussian09[1] with the

b3lyp[2] functional and the LANL2DZ[3] pseudopotential for Au and Ag and the 6-311+G(d,p) basis set

for all other atoms. All optimized geometries were verified by frequency calculations as minima (zero

imaginary frequency). Entropic corrections to the free energies were calculated using Truhlar’s quasi-

harmonic approximation (vibrational frequencies lower than 100 cm-1 are set equal to 100 cm-1 to

correct for the breakdown of the harmonic oscillator approximation for low frequencies).[4]

GaussView 5.0[5] was used to generate input and visualize output structures. CYLview[6] was used to

render the computed structures.

(1) M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani,

V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F.

Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa,

M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Jr. Montgomery, J. E. Peralta, F.

Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J.

Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M.

Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E.

Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma,

V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B.

Foresman, J. V. Ortiz, J. Cioslowski and D. J. Fox, Gaussian 09, revision D.01; Gaussian, Inc.:

Wallingford, CT, 2013.

(2) (a) S. H. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 1980, 58, 1200-1211; (b) C. Lee, W. Yang, R. G.

Parr, Phys. Rev. B 1988, 37, 785-789; (c) A. D. Becke, J. Chem. Phys., 1993, 98, 5648-5652; (d) P. J.

Stephens, F. J. Devlin, C. F. Chabalowski, M. J. Frisch, J. Phys. Chem. 1994, 98, 11623-11627.

(3) (a) P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 270-283; (b) W. R. Wadt, P. J. Hay, J. Chem.

Phys. 1985, 82, 284-298; (c) P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 299-310.

(4) (a) R. F. Ribeiro, A. V. Marenich, C. J. Cramer, D. G. Truhlar, J. Phys. Chem. B 2011, 115, 14556-

14562; (b) Y. Zhao, D. G. Truhlar, Phys. Chem. Chem. Phys. 2008, 10, 2813-2818.

(5) R. Dennington, T. Keith, J. Millam, GaussView, version 5.0, Semichem Inc., Shawnee Mission, KS,

2009.

(6) C. Y. Legault, CYLview, version 1.0b, Université de Sherbrooke, Sherbrooke, Québec, Canada,

2009.

S5

Figure S1: Conformational analysis of 1a.

1a –gauche

S 2.72772 -0.46868 -0.20789

F 0.25691 -0.32753 1.72819

C 3.29598 -2.18582 0.15119

H 4.27933 -2.32238 -0.29994

H 3.38110 -2.32359 1.23118

C 2.23189 -3.10569 -0.44684

H 2.31448 -4.12189 -0.04847

H 2.36252 -3.16270 -1.53232

C 0.87673 -2.47860 -0.10923

H 0.67593 -2.58871 0.95951

H 0.05901 -2.96159 -0.64880

C 0.94763 -0.97777 -0.45081

H 0.73338 -0.81424 -1.50777

C -0.03275 -0.09947 0.36290

C -1.49990 -0.49750 0.16025

C -1.99581 -0.94329 -1.06944

H -1.33633 -1.06192 -1.92053

C -3.34724 -1.25030 -1.22496

H -3.70961 -1.59651 -2.18653

C -4.22483 -1.11921 -0.15237

S6

H -5.27489 -1.36043 -0.27227

C -3.73958 -0.67668 1.07692

H -4.41232 -0.57107 1.92077

C -2.39116 -0.36650 1.23139

H -2.02242 -0.02562 2.18983

C 0.17567 1.39423 0.09287

C -0.20836 1.95598 -1.12946

H -0.69069 1.34584 -1.88397

C 0.00667 3.30691 -1.38836

H -0.29679 3.72495 -2.34168

C 0.60091 4.11946 -0.42418

H 0.76483 5.17250 -0.62334

C 0.97995 3.56751 0.79641

H 1.44432 4.18964 1.55349

C 0.77288 2.21293 1.05440

H 1.08038 1.78737 1.99942

SCF energy: -1156.306436 hartree

zero-point correction: +0.294841 hartree

enthalpy correction: +0.312112 hartree

free energy correction: +0.249581 hartree

quasiharmonic free energy correction: +0.252891 hartree

1a +gauche

S -2.37050 -1.40404 0.97510

F 0.18684 0.00578 2.09577

C -2.98666 -2.23621 -0.55160

H -3.75552 -2.95451 -0.26564

H -3.43617 -1.49882 -1.22193

S7

C -1.76352 -2.89886 -1.18862

H -1.95369 -3.16715 -2.23252

H -1.52322 -3.82001 -0.64887

C -0.60299 -1.90531 -1.06601

H -0.73518 -1.09000 -1.78016

H 0.35626 -2.37397 -1.29588

C -0.60046 -1.38025 0.38351

H -0.07657 -2.10625 1.00826

C 0.14643 -0.05366 0.66565

C -0.46737 1.27235 0.22042

C -1.46703 1.39921 -0.74571

H -1.90269 0.52669 -1.20818

C -1.94112 2.65754 -1.12027

H -2.71996 2.73193 -1.87105

C -1.43111 3.80755 -0.52677

H -1.80483 4.78379 -0.81451

C -0.43909 3.69187 0.44663

H -0.03644 4.57901 0.92255

C 0.03929 2.43815 0.81117

H 0.80857 2.35670 1.56900

C 1.59856 -0.19723 0.19812

C 2.01539 0.29452 -1.04252

H 1.32086 0.84487 -1.66582

C 3.32399 0.09738 -1.47959

H 3.63165 0.48774 -2.44327

C 4.23637 -0.58569 -0.67798

H 5.25646 -0.73216 -1.01476

C 3.83063 -1.07062 0.56401

H 4.53561 -1.59432 1.20012

C 2.51987 -0.88272 0.99780

H 2.21417 -1.24914 1.96957

S8






1a anti

S 0.95786 -1.90251 -1.17452

F -0.25178 0.09765 2.16356

C 2.76407 -2.18924 -0.92029

H 3.04700 -3.08479 -1.47420

H 3.32453 -1.33811 -1.31222

C 2.94472 -2.33225 0.59047

H 3.99390 -2.21039 0.87688

H 2.62703 -3.32995 0.90938

C 2.06027 -1.25970 1.23142

H 2.49307 -0.27512 1.03798

H 1.98156 -1.38043 2.31363

C 0.66698 -1.35302 0.58521

H 0.10106 -2.14779 1.07431

C -0.18738 -0.06520 0.73667

C -1.64331 -0.20307 0.29285

C -2.18415 -1.38538 -0.21738

H -1.56485 -2.26040 -0.36767

C -3.53629 -1.46072 -0.55731

H -3.93433 -2.38529 -0.96012

C -4.36811 -0.36085 -0.37727

H -5.41873 -0.42163 -0.63824

S9

C -3.83985 0.82209 0.14146

H -4.47926 1.68528 0.28876

C -2.49095 0.89999 0.46706

H -2.08778 1.82347 0.86519

C 0.47166 1.19345 0.17615

C 0.40385 1.48068 -1.19235

H -0.13911 0.82036 -1.85541

C 1.02380 2.61542 -1.70948

H 0.96156 2.82103 -2.77231

C 1.71094 3.48807 -0.86701

H 2.18716 4.37495 -1.27001

C 1.77118 3.21684 0.49735

H 2.29285 3.89382 1.16487

C 1.15833 2.07604 1.01592

H 1.19999 1.87747 2.07862






S10

Figure S2: Conformational analysis of 2.

trans-2 –gauche

Au -2.45432 -0.09345 0.12750

F 2.37607 -0.39005 -1.89162

S -0.67219 -0.54262 -1.37098

Cl -4.17154 0.39339 1.62443

C 0.78722 -0.95545 -0.23804

H 0.44992 -0.73572 0.77127

C 1.03546 -2.46732 -0.40282

H 1.45839 -2.87410 0.51740

H 1.76317 -2.62822 -1.20126

C -0.28780 -3.14452 -0.77283

H -0.12917 -4.17433 -1.10482

S11

H -0.96489 -3.17062 0.08559

C -0.90256 -2.30520 -1.88881

H -1.96526 -2.47548 -2.04870

H -0.36682 -2.42424 -2.83219

C 2.00610 -0.06754 -0.56357

C 1.72388 1.43379 -0.52675

C 2.43569 2.27536 -1.38892

H 3.13822 1.84833 -2.09254

C 2.23571 3.65197 -1.35632

H 2.79030 4.28916 -2.03588

C 1.32638 4.21051 -0.45906

H 1.16906 5.28271 -0.43666

C 0.61674 3.38096 0.40369

H -0.10182 3.79935 1.09872

C 0.81449 2.00077 0.37156

H 0.23701 1.38530 1.05083

C 3.18057 -0.44337 0.34822

C 4.31578 -1.07061 -0.17022

H 4.37767 -1.27831 -1.22987

C 5.37282 -1.42031 0.67040

H 6.25021 -1.90097 0.25243

C 5.30515 -1.15522 2.03517

H 6.12703 -1.42843 2.68691

C 4.17424 -0.52866 2.55730

H 4.11314 -0.30934 3.61715

C 3.12163 -0.17107 1.71976

H 2.26260 0.33759 2.14141




S12



trans-2 +gauche

Au 2.70650 -0.02722 -0.21173

F -1.19830 -0.40907 -1.60461

S 0.65469 1.13739 0.01690

Cl 4.74753 -1.12451 -0.44293

C -0.57989 -0.14892 0.64429

H -0.04010 -1.08966 0.56949

C -0.85815 0.21933 2.11320

H -1.11319 -0.67382 2.68670

H -1.71204 0.89706 2.16781

C 0.37721 0.92402 2.68780

H 0.15525 1.38695 3.65340

H 1.19591 0.21472 2.83677

C 0.78407 1.97580 1.66124

H 1.80164 2.34417 1.77344

H 0.09051 2.81837 1.64178

C -1.79493 -0.23288 -0.31882

C -2.66111 -1.47741 -0.10732

C -3.80954 -1.61581 -0.89966

H -4.07953 -0.82642 -1.59042

C -4.60085 -2.75554 -0.81701

H -5.48108 -2.84436 -1.44344

C -4.26320 -3.78081 0.06648

H -4.88127 -4.66867 0.13521

C -3.12301 -3.65864 0.85319

H -2.84374 -4.45267 1.53618

S13

C -2.32331 -2.51858 0.76089

H -1.43260 -2.46955 1.37276

C -2.61449 1.05543 -0.37381

C -2.34014 2.03130 -1.33737

H -1.56831 1.85343 -2.07304

C -3.07007 3.21919 -1.36775

H -2.84980 3.96100 -2.12704

C -4.07810 3.45115 -0.43537

H -4.64543 4.37452 -0.46232

C -4.36272 2.48090 0.52399

H -5.15634 2.64308 1.24456

C -3.64084 1.29000 0.55027

H -3.89730 0.53085 1.27997






trans-2 anti

Au -2.44014 -0.19696 -0.24540

F 2.46827 0.34103 2.21289

S -0.20892 -0.93579 -0.57175

Cl -4.62770 0.53993 0.04685

C 0.68546 -0.57852 1.05192

H -0.00860 0.00853 1.64794

C 0.91095 -1.95060 1.71795

H 0.91697 -1.82903 2.80202

S14

H 1.88475 -2.34850 1.42554

C -0.18674 -2.91247 1.25236

H 0.04713 -3.94508 1.52613

H -1.14960 -2.65617 1.70266

C -0.26959 -2.76115 -0.26268

H -1.18457 -3.14534 -0.70920

H 0.59576 -3.19447 -0.76729

C 1.97813 0.26812 0.86805

C 3.05174 -0.43190 0.03563

C 4.09271 -1.13152 0.65514

H 4.15627 -1.14835 1.73502

C 5.06213 -1.78192 -0.10791

H 5.86735 -2.31081 0.38955

C 5.00212 -1.74748 -1.49862

H 5.75693 -2.25185 -2.09115

C 3.97270 -1.04544 -2.12349

H 3.92496 -0.99707 -3.20548

C 3.00872 -0.38721 -1.36350

H 2.23392 0.17861 -1.86461

C 1.74968 1.71555 0.43824

C 0.48353 2.29817 0.34120

H -0.41809 1.72666 0.52262

C 0.34185 3.64499 0.00435

H -0.65156 4.07103 -0.07410

C 1.46556 4.43177 -0.22315

H 1.35529 5.47881 -0.48144

C 2.73580 3.86458 -0.11518

H 3.61874 4.47020 -0.28522

C 2.87508 2.51976 0.20707

H 3.86578 2.08855 0.28486

S15






cis-2 -gauche

Au -2.16842 -0.16956 -0.14163

F 0.82970 -0.22493 -1.36505

S -0.66281 -1.17548 1.38974

Cl -3.76013 0.75616 -1.57096

C 1.12813 -1.18438 0.77880

H 1.70497 -1.08080 1.69875

C 1.35024 -2.58195 0.18841

H 2.41600 -2.81988 0.18050

H 0.99423 -2.59912 -0.84431

C 0.54905 -3.57037 1.03876

H 0.53041 -4.56702 0.59033

H 0.99689 -3.66595 2.03318

C -0.86870 -3.01078 1.15004

H -1.42653 -3.38784 2.00636

H -1.44492 -3.17311 0.24186

C 1.50751 -0.01156 -0.14931

C 1.09686 1.36380 0.37507

C 0.72359 2.35530 -0.53793

H 0.68045 2.12230 -1.59335

C 0.38015 3.62867 -0.09407

H 0.07623 4.38004 -0.81350

C 0.41218 3.93409 1.26516

S16

H 0.13929 4.92512 1.60889

C 0.78403 2.95333 2.18006

H 0.80142 3.17489 3.24109

C 1.12333 1.67531 1.73844

H 1.39439 0.92906 2.47599

C 3.01260 -0.07525 -0.45524

C 3.46072 -0.42166 -1.73248

H 2.74326 -0.62640 -2.51536

C 4.82687 -0.49255 -2.00467

H 5.15827 -0.75544 -3.00296

C 5.75967 -0.22638 -1.00628

H 6.82089 -0.28146 -1.22014

C 5.31779 0.12156 0.26937

H 6.03414 0.34251 1.05254

C 3.95474 0.20147 0.54140

H 3.63287 0.50313 1.53110






cis-2 +gauche

Au 2.20053 -0.20987 -0.31257

F -1.28431 -0.08481 -1.76092

S 0.56744 -1.91788 -0.53348

Cl 3.93976 1.34207 -0.16556

C -1.12098 -1.44207 0.15192

S17

H -1.74630 -2.23114 -0.27147

C -0.98838 -1.64711 1.66107

H -1.96350 -1.62903 2.15374

H -0.38515 -0.84576 2.09345

C -0.29926 -3.00282 1.84163

H -0.00280 -3.17035 2.87970

H -0.98809 -3.80701 1.56587

C 0.93366 -3.03068 0.92648

H 1.14987 -4.02165 0.52946

H 1.82143 -2.64127 1.41697

C -1.68202 -0.10184 -0.39266

C -3.21659 -0.06889 -0.41951

C -3.81816 1.00501 -1.09072

H -3.19430 1.76460 -1.54578

C -5.20083 1.10215 -1.18347

H -5.64512 1.93676 -1.71372

C -6.01449 0.13489 -0.59166

H -7.09360 0.21410 -0.65677

C -5.42949 -0.93116 0.08157

H -6.04951 -1.69044 0.54458

C -4.03879 -1.03601 0.16098

H -3.62143 -1.88553 0.68552

C -1.12841 1.15699 0.27124

C -0.18418 1.95523 -0.37801

H 0.15636 1.68684 -1.36818

C 0.30793 3.10824 0.23511

H 1.05790 3.70078 -0.27439

C -0.14162 3.47747 1.49779

H 0.24661 4.36970 1.97529

C -1.09709 2.69409 2.14592

H -1.46474 2.98149 3.12456

S18

C -1.59115 1.54589 1.53493

H -2.35688 0.96571 2.03722






cis-2 anti

Au 1.78279 0.50814 -0.24285

F -3.17708 -1.55787 -0.13459

S 0.42219 -0.56212 -1.85641

Cl 3.24442 1.63206 1.18750

C -1.19579 -1.36100 -1.28586

H -1.83346 -1.22536 -2.16182

C -0.86686 -2.85175 -1.14314

H -1.78820 -3.43381 -1.20015

H -0.40577 -3.04508 -0.17200

C 0.11184 -3.21328 -2.26270

H 0.50229 -4.22731 -2.14475

H -0.38501 -3.16254 -3.23658

C 1.24792 -2.19623 -2.19337

H 1.80529 -2.08487 -3.12262

H 1.93785 -2.40584 -1.37887

C -1.99417 -0.73510 -0.10120

C -1.37307 -0.92890 1.27821

C -1.58682 -2.11670 1.98967

H -2.22948 -2.88250 1.57601

S19

C -1.01024 -2.30271 3.24382

H -1.19477 -3.22352 3.78589

C -0.20534 -1.31075 3.80246

H 0.24940 -1.46052 4.77508

C 0.00232 -0.12237 3.10902

H 0.62650 0.65813 3.52685

C -0.58936 0.07162 1.86164

H -0.45619 1.02032 1.35851

C -2.49975 0.68455 -0.33971

C -2.22396 1.42749 -1.48944

H -1.58500 1.03738 -2.27109

C -2.76372 2.70376 -1.65993

H -2.52645 3.26811 -2.55439

C -3.59942 3.24664 -0.69080

H -4.01822 4.23757 -0.82397

C -3.89453 2.50670 0.45486

H -4.54847 2.91804 1.21528

C -3.34709 1.24175 0.62920

H -3.57889 0.67594 1.52320






S20

Figure S3: Conformational analysis of trans-[AgI1a]1+ and trans-[AgI1a]2+.

trans-[AgI1a]1+ –gauche

Ag 2.52519 0.22312 -0.63622

S 1.34191 -1.67764 0.61974

C -0.39497 -1.37586 -0.02359

C -1.13217 -2.71176 0.20805

C -0.10728 -3.87920 0.27033

C 1.28946 -3.36982 -0.11283

C -1.04860 -0.12736 0.60866

S21

C -2.43320 0.16641 0.02334

C -2.70980 0.02950 -1.34159

C -3.96842 0.35500 -1.84415

C -4.96498 0.81943 -0.98974

C -4.69588 0.95632 0.37018

C -3.43860 0.63510 0.87548

C -0.12690 1.09744 0.52117

C 0.33046 1.55923 -0.73002

C 1.27022 2.60418 -0.80482

C 1.72676 3.22183 0.37078

C 1.22817 2.80172 1.59828

C 0.31630 1.74308 1.67520

H -0.27683 -1.19694 -1.09203

H -1.85316 -2.85685 -0.59789

H -1.69358 -2.65791 1.13992

H -0.39034 -4.69894 -0.39342

H -0.07359 -4.28296 1.28315

H 1.43384 -3.30031 -1.19135

H 2.09947 -3.95426 0.32151

F -1.21015 -0.41700 1.97387

H -0.08817 1.16250 -1.64839

H 1.57068 2.98598 -1.77455

H 2.43323 4.04103 0.31363

H 1.55193 3.29064 2.50946

H -0.03574 1.40787 2.64120

H -3.24329 0.73744 1.93460

H -5.46636 1.31228 1.04391

H -5.94429 1.06889 -1.38032

H -4.16924 0.23830 -2.90263

H -1.96094 -0.33951 -2.03344

S22






trans-[AgI1a]1+ +gauche

Ag 2.66040 -0.22331 -1.27037

S 1.88275 -0.19164 1.13380

C 0.17034 -0.88406 0.80382

C -0.34258 -1.28565 2.19823

C 0.87835 -1.73475 3.05776

C 2.18001 -1.64439 2.23520

C -0.68530 -0.02539 -0.14340

C -0.80360 1.46593 0.10748

C -0.52823 2.07326 1.33645

C -0.69387 3.44944 1.49869

C -1.12721 4.23403 0.43520

C -1.40428 3.63689 -0.79528

C -1.25247 2.26500 -0.95568

C -2.01693 -0.72421 -0.38150

C -3.18185 -0.26273 0.23945

C -4.38353 -0.94948 0.07655

C -4.43577 -2.09405 -0.71495

C -3.27939 -2.55404 -1.34357

C -2.07414 -1.87923 -1.17237

H 0.35503 -1.80422 0.24650

H -1.06531 -2.09392 2.07848

H -0.86720 -0.46311 2.68209

S23

H 0.75645 -2.75822 3.41799

H 0.96527 -1.09548 3.93711

H 2.35566 -2.52951 1.62422

H 3.06212 -1.44246 2.84056

F 0.06958 -0.14204 -1.41378

H -3.15797 0.63575 0.84342

H -5.28016 -0.58105 0.56073

H -5.37312 -2.62105 -0.84835

H -3.31627 -3.43636 -1.97169

H -1.18682 -2.23544 -1.68128

H -1.48228 1.80678 -1.90973

H -1.74777 4.23973 -1.62764

H -1.25378 5.30260 0.56301

H -0.48163 3.90316 2.45954

H -0.18845 1.49380 2.18291






trans-[AgI1a]1+ anti

Ag -2.65367 -0.21172 -0.26306

S -0.54886 -1.60401 -0.77328

C 0.39315 -1.21242 0.80216

C 1.36526 -2.39535 1.01830

C 0.92821 -3.60550 0.15106

C -0.51114 -3.39639 -0.33185

S24

C 0.98176 0.23165 0.87635

C -0.08628 1.25983 0.47791

C -1.25838 1.35168 1.25868

C -2.32554 2.17213 0.85115

C -2.20992 2.94022 -0.32195

C -1.02763 2.89878 -1.05061

C 0.02461 2.06413 -0.65478

C 2.33163 0.43837 0.20309

C 2.57875 -0.00543 -1.10279

C 3.81522 0.22208 -1.70406

C 4.81970 0.89461 -1.01124

C 4.57911 1.33913 0.28608

C 3.34350 1.11540 0.89124

H -0.36594 -1.23756 1.58426

H 1.35526 -2.64789 2.07991

H 2.38362 -2.10198 0.76734

H 0.99935 -4.54396 0.70525

H 1.58409 -3.69408 -0.71712

H -1.25175 -3.58990 0.44460

H -0.76140 -3.96998 -1.22350

F 1.16745 0.39201 2.27576

H 1.81435 -0.52955 -1.66324

H 3.99178 -0.12932 -2.71401

H 5.78151 1.06896 -1.47880

H 5.35404 1.86123 0.83490

H 3.17116 1.45867 1.90225

H 0.93196 2.03874 -1.24366

H -0.91382 3.51702 -1.93304

H -3.02241 3.58908 -0.62636

H -3.19367 2.28367 1.49201

H -1.31309 0.83647 2.21113

S25






cis-[AgI1a]1+ –gauche

Ag -2.37861 0.11279 -0.54463

S -1.42008 -1.60362 1.11700

F 0.36694 -0.59964 -1.35553

C 0.42766 -1.29529 0.91495

C 1.01030 -2.67600 0.54062

C -0.01512 -3.44821 -0.29795

C -1.36269 -3.32397 0.40936

C 0.78394 -0.15315 -0.07451

C 2.29734 0.07823 -0.13317

C 3.02592 0.35309 1.03022

C 4.39856 0.57619 0.96682

C 5.06043 0.53173 -0.25870

C 4.34014 0.26203 -1.41869

C 2.96547 0.03608 -1.36018

C 0.02982 1.15564 0.18527

C -0.06484 1.71488 1.46507

C -0.72893 2.92332 1.66711

C -1.32825 3.59507 0.60215

C -1.24482 3.05776 -0.67873

C -0.56489 1.84719 -0.89696

H 0.76767 -0.99509 1.90411

S26

H 1.22009 -3.22389 1.46305

H 1.95754 -2.55477 0.01369

H 0.26406 -4.50080 -0.38810

H -0.07536 -3.03022 -1.30351

H -1.44597 -3.99866 1.26199

H -2.22252 -3.46725 -0.24239

H 2.41945 -0.17820 -2.26855

H 4.84541 0.22472 -2.37660

H 6.12864 0.70598 -0.30709

H 4.94913 0.78469 1.87648

H 2.54029 0.39951 1.99774

H 0.37929 1.21875 2.31855

H -0.78181 3.33912 2.66639

H -1.84189 4.53406 0.76815

H -1.67138 3.58636 -1.52343

H -0.39918 1.50191 -1.91106






cis-[AgI1a]1+ +gauche

Ag 2.48224 0.15804 -0.15372

S 1.25044 -1.96035 -0.88360

F -0.87521 -0.09288 -2.01134

C -0.46603 -1.53074 -0.23032

C -0.54565 -2.02710 1.24286

S27

C 0.82006 -2.56654 1.70921

C 1.53178 -3.15700 0.49643

C -0.95285 -0.09747 -0.59060

C -0.13563 1.11704 -0.14254

C 0.56113 1.18678 1.08484

C 1.26478 2.35196 1.44443

C 1.26473 3.46111 0.59923

C 0.56083 3.40359 -0.60167

C -0.12334 2.24616 -0.97211

C -2.43079 0.02521 -0.21315

C -2.84924 0.70604 0.93403

C -4.20158 0.75660 1.26867

C -5.14800 0.13713 0.45677

C -4.73760 -0.53448 -0.69375

C -3.38739 -0.59567 -1.02644

H -1.10803 -2.16006 -0.84574

H -1.28558 -2.82830 1.28136

H -0.91623 -1.24727 1.90784

H 0.69678 -3.32234 2.48868

H 1.43383 -1.76788 2.13756

H 1.09260 -4.10513 0.18035

H 2.60379 -3.29725 0.62837

H -0.65627 2.21682 -1.91289

H 0.54020 4.26485 -1.25894

H 1.79288 4.36285 0.88442

H 1.76699 2.39418 2.40423

H 0.49066 0.38368 1.80726

H -2.13367 1.21584 1.56770

H -4.51355 1.29115 2.15815

H -6.19965 0.18460 0.71334

H -5.46943 -1.00733 -1.33801

S28

H -3.08194 -1.10071 -1.93448






cis-[AgI1a]1+ anti

Ag 1.49607 0.45217 -1.44703

S 0.79117 -1.92342 -0.80360

F -1.22625 -0.45393 2.45600

C -0.09581 -1.69770 0.84675

C 0.94760 -2.08080 1.93582

C 2.37050 -2.04955 1.36703

C 2.29972 -2.66487 -0.02383

C -0.87748 -0.35103 1.08142

C -2.19565 -0.26370 0.31666

C -2.50079 -1.04896 -0.79802

C -3.72863 -0.90959 -1.44883

C -4.66654 0.00704 -0.98662

C -4.37359 0.78870 0.13167

C -3.14792 0.65896 0.77405

C -0.04528 0.92881 0.95647

C -0.13423 1.74110 -0.19834

C 0.67507 2.88673 -0.33309

C 1.54943 3.25046 0.69558

C 1.59037 2.48626 1.85723

C 0.80516 1.33691 1.98602

S29

H -0.87526 -2.45789 0.82170

H 0.71693 -3.09591 2.26695

H 0.84273 -1.44414 2.81114

H 3.05967 -2.61313 2.00103

H 2.74721 -1.02408 1.30618

H 2.13672 -3.74303 0.01049

H 3.15837 -2.45729 -0.66062

H -2.93584 1.26182 1.64889

H -5.10353 1.49616 0.50705

H -5.62253 0.10753 -1.48666

H -3.94997 -1.52951 -2.30961

H -1.80543 -1.78777 -1.17687

H -0.91461 1.54921 -0.92772

H 0.55558 3.52519 -1.20136

H 2.15585 4.14330 0.60355

H 2.22992 2.78733 2.67869

H 0.83510 0.77777 2.91114






[AgI21a]2+ –gauche

Ag 2.18388 1.66949 -0.78404

Ag 1.26799 -2.32271 1.38000

S 1.34585 -0.98237 -0.84838

F -0.92902 -0.98339 1.22923

S30

C -0.50618 -0.65621 -1.08645

C -1.02439 -1.99025 -1.62375

C -0.04754 -2.42056 -2.72662

C 1.40218 -2.26611 -2.22774

C -1.16398 -0.04649 0.16838

C -2.67677 0.08091 -0.01348

C -3.19310 0.84157 -1.07110

C -4.56909 0.96791 -1.23780

C -5.44244 0.34203 -0.34949

C -4.93208 -0.41028 0.70446

C -3.55463 -0.54436 0.87648

C -0.52215 1.27313 0.61313

C -0.14912 2.26557 -0.32741

C 0.41346 3.48799 0.10771

C 0.59907 3.72837 1.47462

C 0.19121 2.76898 2.39418

C -0.36250 1.55549 1.96955

H -0.54843 0.08507 -1.88542

H -2.03382 -1.86301 -2.01826

H -1.08217 -2.73287 -0.82195

H -0.19539 -1.79643 -3.61098

H -0.21854 -3.45450 -3.03192

H 2.09092 -1.90069 -2.98679

H 1.81110 -3.17201 -1.78593

H -0.68748 0.83607 2.70977

H 0.28879 2.96391 3.45572

H 1.01365 4.67158 1.80871

H 0.60938 4.27204 -0.61631

H -0.43440 2.17805 -1.37082

H -2.54245 1.34750 -1.77624

H -4.95756 1.55727 -2.05955

S31

H -6.51314 0.44300 -0.47871

H -5.60441 -0.89777 1.40016

H -3.17811 -1.13327 1.70140






[AgI21a]2+ +gauche

Ag 1.23124 -2.70383 -1.16076

Ag 2.14300 1.59846 0.42041

S 1.35910 -0.98575 0.79222

F -0.86310 -1.01488 -1.26742

C -0.51007 -0.75547 1.01610

C -0.71020 -0.26263 2.47072

C 0.58318 -0.50345 3.29506

C 1.49366 -1.50102 2.57362

C -1.17745 -0.05822 -0.19229

C -0.59389 1.26903 -0.67059

C -0.18107 2.28737 0.22321

C 0.34757 3.50228 -0.27083

C 0.44733 3.71578 -1.65068

C -0.00385 2.73270 -2.52459

C -0.51396 1.52301 -2.04181

C -2.68458 -0.05525 -0.01985

C -3.40548 1.13873 0.09918

C -4.78502 1.10923 0.29537

S32

C -5.45775 -0.10762 0.36270

C -4.74803 -1.30194 0.23140

C -3.37045 -1.27877 0.04798

H -0.87402 -1.78119 0.96516

H -1.54550 -0.82662 2.88772

H -1.00352 0.78375 2.51712

H 0.35294 -0.88432 4.29253

H 1.12277 0.43620 3.43876

H 1.14455 -2.53167 2.63928

H 2.53978 -1.45237 2.87173

H -2.84269 -2.21678 -0.08091

H -5.27013 -2.25051 0.26549

H -6.53122 -0.12773 0.50715

H -5.33270 2.03958 0.38430

H -2.90904 2.09809 0.02958

H -0.39035 2.21452 1.28342

H 0.59122 4.29828 0.42460

H 0.83430 4.65442 -2.02835

H 0.02952 2.90404 -3.59407

H -0.86256 0.77789 -2.74420






[AgI21a]2+ anti

Ag -2.59915 -0.99479 -0.72683

S33

Ag 2.23976 -0.83687 -1.22242

S -0.03480 -1.69156 -0.01977

F -0.05848 1.43646 2.57832

C -0.00413 -0.60330 1.50643

C 1.12910 -1.20620 2.33624

C 0.85726 -2.71870 2.37743

C 0.44748 -3.21882 0.97383

C -0.01624 0.94046 1.25639

C -1.31542 1.43509 0.59675

C -2.55585 0.81620 0.91065

C -3.76137 1.29750 0.35990

C -3.75139 2.41366 -0.48474

C -2.55094 3.06809 -0.72503

C -1.34912 2.58473 -0.18996

C 1.27952 1.44281 0.61782

C 2.32362 1.89108 1.42633

C 3.54801 2.28351 0.87116

C 3.75847 2.22963 -0.50114

C 2.71406 1.81964 -1.33942

C 1.47389 1.43169 -0.78448

H -0.93783 -0.83746 2.01773

H 1.12554 -0.77856 3.34039

H 2.10383 -0.98676 1.88868

H 0.04902 -2.92415 3.08219

H 1.73181 -3.27129 2.72440

H -0.40587 -3.89337 0.98672

H 1.25723 -3.69008 0.42077

H 0.63416 1.27060 -1.45316

H 2.81953 1.89283 -2.41688

H 4.70354 2.54472 -0.92654

H 4.33473 2.64084 1.52503

S34

H 2.18231 1.95486 2.49712

H -2.62429 0.09723 1.72177

H -4.70300 0.85776 0.67087

H -4.67854 2.79225 -0.89748

H -2.53832 3.97172 -1.32296

H -0.44137 3.14107 -0.38180






S35

NMR Spectra of Complexes 2 & 3

1H NMR (600 MHz) Spectrum of Complex 2

13C NMR (151 MHz) Spectrum of Complex 2

S36

19F NMR (564 MHz) Spectrum of Complex 2

HSQC Spectrum of Complex 2

S37

HMBC Spectrum of Complex 2

Variable Temperature 1H NMR (600 MHz) of Complex 2

S38

1H NMR (600 MHz) Spectrum of Complex 3

13C NMR (151 MHz) Spectrum of Complex 3

S39

19F NMR (564 MHz) Spectrum of Complex 3

Stacked 1H NMR (600 MHz) Spectra of 1a, 3, 2

Supporting Information: The Sulfur-Fluorine Gauche Effect ...€¦ · All reactions were performed...

Documents

Transcript of Supporting Information: The Sulfur-Fluorine Gauche Effect ...€¦ · All reactions were performed...