Supporting Information ForSupporting Information For 4-Halo-1,2,3-triazolylidenes: Stable Carbenes Featuring Halogen Bonding Xingyu Xu, Zengyu Zhang, Shiqing Huang, Lei Cao, Wei Liu

Supporting Information

For

4-Halo-1,2,3-triazolylidenes: Stable Carbenes Featuring Halogen Bonding

Xingyu Xu, Zengyu Zhang, Shiqing Huang, Lei Cao, Wei Liu and Xiaoyu Yan*

Department of Chemistry, Renmin University of China, Beijing 100872, People’s

Republic of China.

Email: [email protected]

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2019

Contents

1 X-ray Structural Study Details ............................................................................................ 1

2 Computational Details ......................................................................................................... 1

3 Huynh’s Electronic Parameter (HEP) Details ................................................................... 3

4 References ............................................................................................................................. 3

5 Copies of 1H NMR and 13C NMR Spectra .......................................................................... 4

1 X-ray Structural Study Details

All crystallographic data for structures were collected using Bruker D8 venture

Kappa Duo diffractometer equipped with a PHOTON 100 detector, a IµS micro-focus

sealed X-ray tube and a Cryostream Cooler (Oxford Cryosystems) using Mo Kα

radiation (λ = 0.71073 Å). The crystals were mounted in Cryo-Loops using Paratone

oil. The frames were integrated using the SAINT algorithm[1] to give the hkl files

corrected for Lp/decay. Data were corrected for absorption effects using the multi-scan

method (SADABS). [2]

The structures were solved by direct methods using SHELXT[3] and refined

against F2 on all data by full-matrix least squares with SHELXL[4] following established

refinement strategies[5] via the OLEX-2 suite of crystallographic programs. [6] All non-

hydrogen atoms were refined anisotropically ORTEP drawings were prepared using the

ORTEP-3 for Windows (version 2014.1). [7] A very large solvent accessible void in 1-

Au, 2-Au and 3-Au(I) were squeezed by using Platon. [8] In all of the structures, the

commands DELU, SIMU and ISOR were applied to mostly restrain the disorders of

anions, 2,6-diisopropylphenyl substituents and the solvent molecules. Crystallographic

data have been deposited with the Cambridge Crystallographic Data Centre as

supplementary publication nos. CCDC Number: 1-(H+), 1857789. 2-(H+), 1857790. 2,

1857791. 1-Au, 1857792. 2-Au, 1857793. 3-Au(I), 1857794. 1-Cu, 1857795. 2-Cu,

1857796. 3-Cu, 1857797. 5-(I-), 1857798. 3-Ir, 1857800,3-Au[PF6], 1885414. 7,

1868802. 4, 1897693. 5, 1897694. Copies of these data can be obtained free of charge

from the Cambridge Crystallographic Data Centre via

www.ccdc.cam.ac.uk/data_request/cif.

2 Computational Details

Calculations were carried out with the TURBOMOLE program. [9] In order to

reduce the computational cost, the 2,6-diisopropylphenyl groups were replaced by

methyl groups. Geometry optimizations were performed with the density functional

theory (DFT)/B3LYP, together with def-TZVP basis set. Frequency calculations at the

same level of theory were performed.

S1

Figure S1 Cl substitution 1,2,3-triazol-5-ylidene orbital energies ε at the DFT B3LYP/

def-TZVP level of theory.

Figure S2 Br substitution 1,2,3-triazol-5-ylidene orbital energies ε at the DFT B3LYP/


Figure S3 I substitution 1,2,3-triazol-5-ylidene orbital energies ε at the DFT/B3LYP-

S2


Table S1 Details of Computation

Substitute Energy/hatree Energy/e.V

Orbital HOMO LUMO LUMO+1 HOMO LUMO LUMO+1

H -0.1999 -0.0307 0.0336 -5.439279 -0.83535 0.914256

Cl -0.2146 -0.0378 0.0289 -5.839266 -1.02854 0.786369

Br -0.214 -0.0385 -0.0043 -5.82294 -1.04759 -0.117

I -0.2121 -0.0386 -0.0379 -5.771241 -1.05031 -1.03126

3 Huynh’s Electronic Parameter (HEP) Details

Solution complex 7 (55 mmol/L, CDCl3) and donors were mixed respectively

and then HEP tests were accomplished by Bruker Avance 100MHz (13C NMR).

The chemical shift data for each HEP test signal are given in units of (ppm) the

residual solvent resonances 77.7. The F-, Cl-, Br- or I- anion is made by using

excessive KF, KCl, KBr, KI exchanging the anion BF4-of 7 in CH3CN for 24 h.

4 References

[1] SAINT V7.68A; Bruker AXS, Madison, WI, 2009.

[2] SADABS V2008/1; Bruker AXS, Madison, WI, 2008.

[3] G. M. Sheldrick, Acta Cryst. A, 2015, 71, 3.

[4] G. M. Sheldrick, Acta Cryst. C, 2015, 71, 3.

[5] P. Müller, Crystallogr. Rev., 2009, 15 (1), 57.

[6] O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,

J. Appl. Cryst., 2009, 42, 339.

[7] L. J. Farrugia, J. Appl. Cryst., 2012, 45, 849.

[8] P. Van der Sluis and A. L. Spek, Acta Cryst. A 1990, 46, 194.

S3

[9] TURBOMOLE V7.0 2015, A development of University of Karlsruhe and

Forschungszentrum Karlsruhe GmbH, 1989- 2007, TURBOMOLE GmbH, since 2007,

Available from http://www.turbomole.com.

S4

http://www.turbomole.com/

9 8 7 6 5 4 3 2 1 ppm

1.155

1.173

1.176

1.194

1.327

1.344

1.355

1.372

2.130

2.147

2.164

2.180

2.197

2.215

2.232

2.252

2.268

2.285

2.302

2.319

2.336

2.353

7.413

7.432

7.462

7.482

7.663

7.683

7.702

7.721

7.740

7.760

9.157

6.39

6.00

6.48

5.99

2.22

2.19

2.12

2.00

1.05

1.02

1.03

PC 1.00GB 0LB 0.30 HzSSB 0WDW EMSF 400.1300091 MHzSI 32768SFO1 400.1326008 MHzPL1W 8.92857742 WPL1 1.80 dBP1 13.10 usecNUC1 1H======== CHANNEL f1 ========

TD0 1D1 2.00000000 secTE 296.8 KDE 6.50 usecDW 78.200 usecRG 406AQ 2.5625076 secFIDRES 0.195125 HzSWH 6393.862 HzDS 0NS 8SOLVENT CDCl3TD 32768PULPROG zg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 14.18Date_ 20171120PROCNO 1EXPNO 1NAME xxy−tcl−p−20171120

1-(H+)

5 Copies of 1H NMR and 13C NMR Spectra

S5

180 160 140 120 100 80 60 40 20 ppm

23.413

23.680

24.740

24.893

28.765

29.015

39.369

39.578

39.787

39.995

40.203

40.412

40.618

125.500

126.017

127.153

130.875

133.898

134.480

134.679

135.778

145.500

146.028

PC 1.40GB 0LB 3.00 HzSSB 0WDW EMSF 100.6127690 MHzSI 32768SFO2 400.1316005 MHzPL13W 0.19265592 WPL12W 0.25809658 WPL2W 8.92857742 WPL13 18.46 dBPL12 17.19 dBPL2 1.80 dBPCPD2 80.00 usecNUC2 1HCPDPRG2 waltz16======== CHANNEL f2 ========

SFO1 100.6238364 MHzPL1W 43.93649673 WPL1 3.00 dBP1 13.50 usecNUC1 13C======== CHANNEL f1 ========

TD0 10D11 0.03000000 secD1 2.00000000 secTE 297.7 KDE 8.00 usecDW 19.800 usecRG 181AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 40SOLVENT DMSOTD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 16.56Date_ 20171116PROCNO 1EXPNO 2NAME xxy−11−11yl

1-(H+)

S6

9 8 7 6 5 4 3 2 1 ppm

1.169

1.183

1.335

1.348

1.352

1.365

2.075

2.092

2.105

2.122

2.139

2.156

2.173

2.190

2.233

2.249

2.266

2.283

2.300

2.317

2.330

7.266

7.412

7.432

7.462

7.481

7.662

7.681

7.701

7.722

7.741

7.761

9.178

6.117

6.284

6.476

6.426

2.264

2.307

2.061

2.095

1.000

1.060

0.915


TD0 1D1 2.00000000 secTE 295.1 KDE 6.50 usecDW 78.200 usecRG 287AQ 2.5625076 secFIDRES 0.195125 HzSWH 6393.862 HzDS 0NS 8SOLVENT CDCl3TD 32768PULPROG zg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 13.26Date_ 20170925PROCNO 1EXPNO 1NAME xxy−dipp−br−20170925

2-(H+)

S7

180 160 140 120 100 80 60 40 20 ppm23.171

23.262

24.715

24.945

29.376

29.597

76.716

77.033

77.351

122.180

125.010

125.326

128.211

130.403

133.625

133.957

135.582

145.102

145.616



TD0 1D11 0.03000000 secD1 2.00000000 secTE 296.2 KDE 8.00 usecDW 19.800 usecRG 114AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 200SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 14.10Date_ 20170925PROCNO 1EXPNO 2NAME xxy−dipp−br−20170925

2-(H+)

S8

9 8 7 6 5 4 3 2 1 ppm

1.053

1.070

1.133

1.142

1.150

1.159

1.227

1.244

2.473

2.490

2.507

2.524

2.541

2.558

2.575

2.892

2.909

2.926

2.944

2.961

2.978

2.995

7.035

7.055

7.141

7.160

7.187

7.206

7.226

7.268

7.287

7.307

6.552

6.064

6.114

6.111

2.042

2.000

2.130

2.294

1.198

1.122


TD0 1D1 2.00000000 secTE 301.3 KDE 6.50 usecDW 78.200 usecRG 80.6AQ 2.5625076 secFIDRES 0.195125 HzSWH 6393.862 HzDS 0NS 8SOLVENT C6D6TD 32768PULPROG zg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 14.03Date_ 20180525PROCNO 1EXPNO 1NAME xxy−525cb−20180525

1

S9

220 200 180 160 140 120 100 80 60 40 20 ppm

23.192

23.912

24.501

24.708

28.937

29.215

123.907

124.430

127.819

128.060

128.300

130.200

130.987

131.707

138.560

139.276

145.426

146.058

198.514



TD0 1D11 0.03000000 secD1 2.00000000 secTE 301.7 KDE 8.00 usecDW 19.800 usecRG 2050AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 64SOLVENT C6D6TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 14.07Date_ 20180525PROCNO 1EXPNO 2NAME xxy−525cb−20180525

1

S10

9 8 7 6 5 4 3 2 1 ppm

1.062

1.079

1.140

1.157

1.178

1.195

1.218

1.235

2.475

2.492

2.509

2.526

2.542

2.903

2.920

2.937

2.954

2.970

7.044

7.063

7.140

7.160

7.195

7.214

7.232

7.269

7.288

7.307

6.410

6.078

6.178

6.208

2.067

2.000

2.070

2.334

1.289

1.176


TD0 1D1 2.00000000 secTE 297.4 KDE 6.50 usecDW 78.200 usecRG 71.8AQ 2.5625076 secFIDRES 0.195125 HzSWH 6393.862 HzDS 0NS 8SOLVENT C6D6TD 32768PULPROG zg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 13.38Date_ 20180524PROCNO 1EXPNO 1NAME xxy−524cbBR−20180524

2

S11

220 200 180 160 140 120 100 80 60 40 20 ppm

23.160

23.939

24.519

24.889

25.837

28.919

29.239

123.905

124.416

125.899

127.822

128.062

128.303

130.192

131.662

131.927

139.155

145.457

145.944

202.672



TD0 1D11 0.03000000 secD1 2.00000000 secTE 297.9 KDE 8.00 usecDW 19.800 usecRG 2050AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 128SOLVENT C6D6TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 13.42Date_ 20180524PROCNO 1EXPNO 2NAME xxy−524cbBR−20180524

2

S12

9 8 7 6 5 4 3 2 1 ppm

1.063

1.078

2.473

7.017

7.160

7.185

7.204

7.223

24.422

4.220

4.320

2.000


TD0 1D1 2.00000000 secTE 297.0 KDE 6.50 usecDW 78.200 usecRG 128AQ 2.5625076 secFIDRES 0.195125 HzSWH 6393.862 HzDS 0NS 8SOLVENT C6D6TD 32768PULPROG zg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 12.29Date_ 20180526PROCNO 1EXPNO 1NAME xxy−18626cbi−20180526

3

S13

220 200 180 160 140 120 100 80 60 40 20 ppm

23.866

25.132

28.921

32.315

68.379

123.926

127.819

128.060

128.301

130.413

145.638



TD0 1D11 0.03000000 secD1 2.00000000 secTE 297.6 KDE 8.00 usecDW 19.800 usecRG 2050AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 128SOLVENT C6D6TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 12.33Date_ 20180526PROCNO 1EXPNO 2NAME xxy−18626cbi−20180526

3

S14

9 8 7 6 5 4 3 2 1 ppm

1.138

1.153

1.285

1.302

1.352

1.369

2.213

2.229

2.246

2.263

2.279

2.378

2.395

2.412

2.429

2.445

7.266

7.314

7.333

7.379

7.398

7.531

7.551

7.570

7.611

7.630

7.650

12.568

6.684

6.275

2.099

2.088

2.125

2.000

1.066

1.012


TD0 1D1 2.00000000 secTE 297.9 KDE 6.50 usecDW 78.200 usecRG 128AQ 2.5625076 secFIDRES 0.195125 HzSWH 6393.862 HzDS 0NS 8SOLVENT CDCl3TD 32768PULPROG zg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 14.09Date_ 20171121PROCNO 1EXPNO 1NAME xxy−11−20−cu−20171121

1-Cu

S15

180 160 140 120 100 80 60 40 20 ppm

23.259

24.248

24.471

24.575

28.903

29.183

76.737

77.055

77.373

124.268

124.669

128.753

131.634

132.612

135.268

138.131

144.749

145.615

168.414



TD0 1D11 0.03000000 secD1 2.00000000 secTE 298.4 KDE 8.00 usecDW 19.800 usecRG 114AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 128SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 14.13Date_ 20171121PROCNO 1EXPNO 2NAME xxy−11−20−cu−20171121

1-Cu

S16

9 8 7 6 5 4 3 2 1 ppm

1.119

1.131

1.135

1.149

1.167

1.315

1.332

2.150

2.167

2.184

2.201

2.219

2.236

2.253

2.270

7.285

7.310

7.329

7.425

7.445

7.607

7.627

7.646

7.674

7.694

7.714

34.714

12.369

8.402

3.815

3.844

2.079

2.000


TD0 1D1 2.00000000 secTE 298.1 KDE 6.50 usecDW 78.200 usecRG 181AQ 2.5625076 secFIDRES 0.195125 HzSWH 6393.862 HzDS 0NS 8SOLVENT CDCl3TD 32768PULPROG zg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 14.24Date_ 20171121PROCNO 1EXPNO 1NAME xxy−11−20−au−20171121

1-Au

S17

180 160 140 120 100 80 60 40 20 ppm

23.154

23.977

24.215

24.609

29.009

29.375

76.713

77.030

77.348

124.509

124.980

128.225

132.229

133.238

134.270

138.450

144.683

145.411

172.588



TD0 1D11 0.03000000 secD1 2.00000000 secTE 298.7 KDE 8.00 usecDW 19.800 usecRG 114AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 248SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 14.27Date_ 20171121PROCNO 1EXPNO 2NAME xxy−11−20−au−20171121

1-Au

S18

9 8 7 6 5 4 3 2 1 ppm

1.151

1.168

1.320

1.337

1.369

1.386

2.179

2.198

2.215

2.232

2.249

2.266

2.360

2.378

2.395

2.412

2.429

2.446

2.463

7.285

7.337

7.356

7.396

7.416

7.557

7.576

7.596

7.631

7.650

7.670

12.501

6.477

6.298

2.173

2.129

1.965

2.004

0.972

1.000


TD0 1D1 2.00000000 secTE 295.2 KDE 6.50 usecDW 78.200 usecRG 181AQ 2.5625076 secFIDRES 0.195125 HzSWH 6393.862 HzDS 0NS 8SOLVENT CDCl3TD 32768PULPROG zg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 13.31Date_ 20170925PROCNO 1EXPNO 1NAME xxy 9−22−dipp−Br−CuI−rongjicanliu

2-Cu

S19

180 160 140 120 100 80 60 40 20 ppm23.105

24.230

24.396

24.659

28.817

29.133

76.680

76.997

77.315

124.204

124.589

125.286

129.705

131.556

132.491

135.047

144.726

145.404

171.840



TD0 10D11 0.03000000 secD1 2.00000000 secTE 297.7 KDE 8.00 usecDW 19.800 usecRG 2050AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 613SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 17.03Date_ 20170925PROCNO 1EXPNO 2NAME xxy−9−22−dbrcu−20170925

2-Cu

S20

9 8 7 6 5 4 3 2 1 ppm

1.110

1.127

1.141

1.316

1.333

2.110

2.127

2.144

2.161

2.181

2.199

2.216

2.233

2.250

7.285

7.297

7.316

7.409

7.429

7.596

7.615

7.635

7.660

7.680

7.700

36.369

12.268

4.219

4.000

4.743

3.949

1.935

2.029


TD0 1D1 2.00000000 secTE 293.9 KDE 6.50 usecDW 78.200 usecRG 80.6AQ 2.5625076 secFIDRES 0.195125 HzSWH 6393.862 HzDS 0NS 8SOLVENT CDCl3TD 32768PULPROG zg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 19.02Date_ 20171110PROCNO 1EXPNO 1NAME xxy−dipp−Br−Au

2-Au

S21

180 160 140 120 100 80 60 40 20 ppm

23.085

24.026

24.253

24.754

28.976

29.371

76.785

77.103

77.306

77.421

124.495

124.950

125.775

129.299

132.174

133.141

134.106

144.686

145.254

176.242



TD0 1D11 0.03000000 secD1 2.00000000 secTE 294.5 KDE 8.00 usecDW 19.800 usecRG 114AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 104SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 19.05Date_ 20171110PROCNO 1EXPNO 2NAME xxy−dipp−Br−Au

2-Au

S22

9 8 7 6 5 4 3 2 1 ppm

1.112

1.122

1.129

1.139

1.325

1.342

2.124

2.141

2.158

2.175

2.192

2.327

2.344

2.361

2.378

2.395

7.261

7.306

7.325

7.372

7.392

7.533

7.552

7.572

7.607

7.627

7.647

6.227

5.806

12.224

1.969

1.993

2.000

2.141

1.082

1.000


TD0 1D1 1.00000000 secTE 294.2 KDE 6.50 usecDW 78.200 usecRG 203AQ 2.5625076 secFIDRES 0.195125 HzSWH 6393.862 HzDS 0NS 8SOLVENT CDCl3TD 32768PULPROG zg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 16.25Date_ 20171011PROCNO 1EXPNO 1NAME xxy−9−25−dipp−2iicu−20171011

3-Cu

S23

180 160 140 120 100 80 60 40 20 ppm

0.959

22.994

24.354

24.905

28.799

29.189

76.651

76.969

77.286

124.226

124.582

131.306

131.542

132.419

134.698

144.756

145.267



TD0 10D11 0.03000000 secD1 2.00000000 secTE 294.8 KDE 8.00 usecDW 19.800 usecRG 2050AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 536SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 16.28Date_ 20171011PROCNO 1EXPNO 2NAME xxy−9−25−dipp−2iicu−20171011

3-Cu

S24

9 8 7 6 5 4 3 2 1 ppm

1.051

1.058

1.079

1.096

1.317

1.334

2.123

2.140

2.157

2.174

2.191

2.202

2.208

2.222

2.240

2.254

2.271

2.288

2.305

2.322

7.150

7.169

7.265

7.334

7.354

7.476

7.496

7.515

7.567

7.586

7.606

11.383

11.142

12.389

12.485

4.248

4.201

3.960

3.828

1.915

2.000


TD0 1D1 2.00000000 secTE 297.7 KDE 6.50 usecDW 78.200 usecRG 287AQ 2.5625076 secFIDRES 0.195125 HzSWH 6393.862 HzDS 0NS 8SOLVENT CDCl3TD 32768PULPROG zg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 15.37Date_ 20180228PROCNO 1EXPNO 1NAME xxy−Au−2

3-Au(I)

S25

180 160 140 120 100 80 60 40 20 ppm

23.386

24.097

24.875

25.077

28.825

29.341

76.841

77.159

77.477

106.111

124.141

124.722

131.256

131.692

132.483

134.425

144.863

145.369

184.190



TD0 10D11 0.03000000 secD1 2.00000000 secTE 298.8 KDE 8.00 usecDW 19.800 usecRG 2050AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 200SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 17.42Date_ 20180228PROCNO 1EXPNO 2NAME xxy−au−i−i−20180228

3-Au(I)

S26

9 8 7 6 5 4 3 2 1 ppm

1.098

1.102

1.118

1.310

1.327

2.036

2.053

2.070

2.087

2.104

2.121

2.169

2.186

2.203

2.220

2.237

2.253

7.254

7.261

7.280

7.371

7.391

7.557

7.577

7.596

7.618

7.637

7.657

35.447

12.079

4.000

4.448

3.567

3.898

2.003

2.034

PC 1.00GB 0LB 0.30 HzSSB 0WDW EMSF 400.1300128 MHzSI 32768SFO1 400.1326008 MHzPL1W 17.01305389 WPL1 −1.00 dBP1 10.40 usecNUC1 1H======== CHANNEL f1 ========

TD0 1D1 1.00000000 secTE 295.8 KDE 6.50 usecDW 78.200 usecRG 114AQ 2.5625076 secFIDRES 0.195125 HzSWH 6393.862 HzDS 0NS 8SOLVENT CDCl3TD 32768PULPROG zg30PROBHD 5 mm PABBO BB−INSTRUM spectTime 17.39Date_ 20181211PROCNO 1EXPNO 1NAME xxy1211pf−3−20181211

3-Au[PF6]

S27

220 200 180 160 140 120 100 80 60 40 20 0 ppm23.084

24.199

24.434

25.077

29.031

29.476

76.841

77.160

77.477

96.809

124.554

124.998

131.106

132.104

133.075

133.913

144.940

145.286

183.513

PC 1.40GB 0LB 3.00 HzSSB 0WDW EMSF 100.6127589 MHzSI 32768SFO2 400.1316005 MHzPL13W 0.38087484 WPL12W 0.28759566 WPL2W 17.01305389 WPL13 15.50 dBPL12 16.72 dBPL2 −1.00 dBPCPD2 80.00 usecNUC2 1HCPDPRG2 waltz16======== CHANNEL f2 ========


TD0 3D11 0.03000000 secD1 2.00000000 secTE 296.8 KDE 6.50 usecDW 19.800 usecRG 181AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 120SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PABBO BB−INSTRUM spectTime 17.44Date_ 20181211PROCNO 1EXPNO 2NAME xxy1211pf−20181211

3-Au[PF6]

S28

9 8 7 6 5 4 3 2 1 ppm

1.330

1.347

1.377

1.394

2.134

2.151

2.168

2.185

2.202

2.219

2.238

2.328

2.345

2.362

2.379

2.396

2.413

2.430

7.262

7.311

7.330

7.385

7.404

7.552

7.572

7.591

7.623

7.643

7.663

12.872

6.444

6.274

2.111

2.132

2.033

2.001

1.043

1.000


TD0 1D1 2.00000000 secTE 296.0 KDE 6.50 usecDW 78.200 usecRG 203AQ 2.5625076 secFIDRES 0.195125 HzSWH 6393.862 HzDS 0NS 8SOLVENT CDCl3TD 32768PULPROG zg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 14.31Date_ 20180317PROCNO 1EXPNO 1NAME xxy−314−c−a−1−20180316

4

S29

180 160 140 120 100 80 60 40 20 ppm

23.057

24.261

24.391

25.002

28.979

29.311

29.704

76.704

77.022

77.339

94.901

124.374

124.729

131.534

131.828

132.680

134.051

144.981

145.330

182.395



TD0 10D11 0.03000000 secD1 2.00000000 secTE 296.9 KDE 8.00 usecDW 19.800 usecRG 2050AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 296SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 14.35Date_ 20180317PROCNO 1EXPNO 2NAME xxy−314−c−a−1−20180316

4

S30

9 8 7 6 5 4 3 2 1 ppm

1.120

1.130

1.137

1.305

1.322

1.395

1.412

2.123

2.140

2.157

2.174

2.191

2.208

2.224

2.331

2.348

2.365

2.382

2.399

2.416

2.434

7.107

7.114

7.125

7.142

7.161

7.178

7.182

7.264

7.298

7.317

7.356

7.376

7.397

7.401

7.521

7.541

7.560

7.598

7.617

7.637

6.000

6.088

6.069

6.188

2.094

2.151

3.073

2.038

4.081

1.060

1.051

PC 1.00GB 0LB 0.30 HzSSB 0WDW EMSF 400.1300091 MHzSI 32768SFO1 400.1326008 MHzPL1W 17.01305389 WPL1 −1.00 dBP1 10.40 usecNUC1 1H======== CHANNEL f1 ========

TD0 1D1 1.00000000 secTE 293.7 KDE 6.50 usecDW 78.200 usecRG 228AQ 2.5625076 secFIDRES 0.195125 HzSWH 6393.862 HzDS 0NS 8SOLVENT CDCl3TD 32768PULPROG zg30PROBHD 5 mm PABBO BB−INSTRUM spectTime 13.27Date_ 20180710PROCNO 1EXPNO 1NAME xxy−7−7−2−20180710

5

S31

180 160 140 120 100 80 60 40 20 ppm

23.060

24.392

24.977

28.961

29.241

76.713

77.030

77.348

97.198

104.841

124.293

124.629

125.899

127.644

131.551

132.292

132.490

134.373

145.052

145.346

186.951

PC 1.40GB 0LB 3.00 HzSSB 0WDW EMSF 100.6127690 MHzSI 32768SFO2 400.1316005 MHzPL13W 0.38087484 WPL12W 0.28759566 WPL2W 17.01305389 WPL13 15.50 dBPL12 16.72 dBPL2 −1.00 dBPCPD2 80.00 usecNUC2 1HCPDPRG2 waltz16======== CHANNEL f2 ========


TD0 3D11 0.03000000 secD1 2.00000000 secTE 294.8 KDE 6.50 usecDW 19.800 usecRG 181AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 368SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PABBO BB−INSTRUM spectTime 13.33Date_ 20180710PROCNO 1EXPNO 2NAME xxy−7−2−2−20180711

5

S32

9 8 7 6 5 4 3 2 1 ppm

1.077

1.094

1.155

1.172

1.343

1.360

1.395

1.411

2.212

2.228

2.245

2.262

2.279

2.522

2.539

2.556

2.572

2.589

2.606

7.261

7.338

7.357

7.381

7.400

7.564

7.583

7.603

7.612

7.631

7.651

6.148

6.179

6.282

6.034

2.071

2.000

2.009

2.029

1.034

1.000


TD0 1D1 2.00000000 secTE 296.9 KDE 6.50 usecDW 78.200 usecRG 203AQ 2.5625076 secFIDRES 0.195125 HzSWH 6393.862 HzDS 0NS 8SOLVENT CDCl3TD 32768PULPROG zg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 17.53Date_ 20171229PROCNO 1EXPNO 1NAME xxy−Ir−2−20171229

3-Ir

S33

180 160 140 120 100 80 60 40 20 ppm22.65

23.58

25.01

26.54

29.06

29.28

98.68

124.10

124.75

131.50

131.71

132.50

134.42

145.68

168.58

174.54

180.44



TD0 1D11 0.03000000 secD1 2.00000000 secTE 297.5 KDE 8.00 usecDW 19.800 usecRG 114AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 528SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 17.55Date_ 20171229PROCNO 1EXPNO 2NAME xxy−Ir−2−20171229

3-Ir

S34

10 9 8 7 6 5 4 3 2 1 ppm

1.187

1.204

1.359

1.376

1.385

1.402

1.623

1.641

2.179

2.196

2.213

2.230

2.246

2.337

2.353

2.370

2.387

2.404

4.925

4.942

4.959

4.977

4.994

7.286

7.381

7.389

7.396

7.404

7.435

7.441

7.454

7.460

7.636

7.644

7.652

7.660

7.675

7.695

7.715

7.735

7.756

5.998

6.000

5.843

6.259

12.077

2.424

2.344

2.156

2.477

4.725

2.427

2.475


TD0 1D1 2.00000000 secTE 299.4 KDE 6.50 usecDW 78.200 usecRG 80.6AQ 2.5625076 secFIDRES 0.195125 HzSWH 6393.862 HzDS 0NS 8SOLVENT CDCl3TD 32768PULPROG zg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 14.20Date_ 20180511PROCNO 1EXPNO 1NAME xxy−5h−bf−20180511

7

S35

180 160 140 120 100 80 60 40 20 ppm

23.025

23.637

24.586

25.246

25.629

29.642

30.004

54.036

77.383

77.701

78.019

97.945

113.492

125.068

125.159

125.505

131.643

132.826

133.110

133.596

134.781

145.700

145.753

184.389

187.349



TD0 10D11 0.03000000 secD1 2.00000000 secTE 297.6 KDE 8.00 usecDW 19.800 usecRG 2050AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 96SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 19.28Date_ 20180425PROCNO 1EXPNO 2NAME xxy−423bf−20180425

7

S36

220 200 180 160 140 120 100 80 60 40 20 ppm

1.51

2.32

22.46

22.96

23.57

24.53

25.18

25.56

29.60

29.96

30.17

53.94

77.38

77.70

78.02

97.86

113.42

117.18

125.10

125.49

131.57

132.74

133.05

133.59

134.75

145.71

184.29

187.31



TD0 10D11 0.03000000 secD1 2.00000000 secTE 297.6 KDE 8.00 usecDW 19.800 usecRG 2050AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 128SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 20.20Date_ 20180426PROCNO 1EXPNO 2NAME xxy−bf−cn−20180426

7 + 5 eq CH3CN

S37

220 200 180 160 140 120 100 80 60 40 20 ppm

77.38

77.70

78.02

104.17

107.00

113.23

124.18

124.88

125.19

132.40

132.95

133.12

136.43

145.60

149.97

150.15

154.64

183.85

187.83



TD0 10D11 0.03000000 secD1 2.00000000 secTE 298.2 KDE 8.00 usecDW 19.800 usecRG 2050AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 152SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 14.18Date_ 20180427PROCNO 1EXPNO 2NAME xxy−bf−dmap−20180427

7 + 5 eq DMAP

S38

220 200 180 160 140 120 100 80 60 40 20 ppm107.91

23.10

23.79

24.65

25.24

25.59

29.51

29.89

54.07

77.38

77.70

78.02

113.38

124.88

125.23

132.17

132.34

133.02

133.16

145.81

183.90

188.54



TD0 1D11 0.03000000 secD1 2.00000000 secTE 296.4 KDE 8.00 usecDW 19.800 usecRG 2050AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 56SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 14.21Date_ 20180518PROCNO 1EXPNO 2NAME xxy−518kbr−20180518

7 + Br-

S39

220 200 180 160 140 120 100 80 60 40 20 ppm

187.66

23.04

23.67

24.61

25.25

25.63

29.62

29.98

54.04

77.38

77.70

78.02

99.56

113.48

125.05

125.12

125.45

131.74

132.74

133.11

133.48

134.83

145.72

184.30



TD0 1D11 0.03000000 secD1 2.00000000 secTE 296.0 KDE 8.00 usecDW 19.800 usecRG 2050AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 72SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 14.38Date_ 20180518PROCNO 1EXPNO 2NAME xxy−518kcl−20180518

7 + Cl-

S40

220 200 180 160 140 120 100 80 60 40 20 ppm23.04

23.66

24.62

25.27

25.66

29.66

30.02

54.06

77.38

77.70

78.02

98.10

113.51

125.08

125.17

125.52

131.67

132.82

133.13

133.60

145.73

184.39

187.38



TD0 1D11 0.03000000 secD1 2.00000000 secTE 295.9 KDE 8.00 usecDW 19.800 usecRG 2050AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 48SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 14.30Date_ 20180518PROCNO 1EXPNO 2NAME xxy−518kf−20180518

7 + F-

S41

220 200 180 160 140 120 100 80 60 40 20 ppm23.17

23.80

24.63

25.22

25.56

29.47

29.85

54.07

77.38

77.70

78.02

110.89

113.33

124.84

125.18

132.25

132.96

133.16

135.13

145.72

145.80

183.74

188.73



TD0 1D11 0.03000000 secD1 2.00000000 secTE 295.8 KDE 8.00 usecDW 19.800 usecRG 2050AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 112SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 14.08Date_ 20180518PROCNO 1EXPNO 2NAME xxy−518ik−20180518

7 + I-

S42

220 200 180 160 140 120 100 80 60 40 20 ppm22.85

23.50

24.41

25.06

25.41

29.42

29.78

33.73

53.67

77.38

77.70

78.02

101.58

113.22

120.67

124.89

125.25

129.51

131.63

132.46

132.90

133.25

134.69

138.19

145.55

183.94

187.49



TD0 1D11 0.03000000 secD1 2.00000000 secTE 295.0 KDE 8.00 usecDW 19.800 usecRG 2050AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 136SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 21.50Date_ 20180518PROCNO 1EXPNO 2NAME xxy−518NMEmz−20180518

7 + 5eq N－methylimidazole

S43

220 200 180 160 140 120 100 80 60 40 20 0 ppm

77.385

77.703

78.022

100.151

113.381

124.289

125.007

125.387

131.711

132.652

133.039

133.417

134.790

136.539

145.694

150.229

184.193

187.491



TD0 10D11 0.03000000 secD1 2.00000000 secTE 297.8 KDE 8.00 usecDW 19.800 usecRG 2050AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 96SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 13.50Date_ 20180427PROCNO 1EXPNO 2NAME xxy−bf−py2−20180427

7 + 5 eq py

S44

200 180 160 140 120 100 80 60 40 20 ppm

98.904

11.863

23.057

23.674

24.629

25.279

25.662

29.671

30.032

46.864

54.066

77.381

77.699

78.017

113.524

125.111

125.167

125.510

131.744

132.803

133.146

133.579

134.866

145.765

184.309

187.480



TD0 10D11 0.03000000 secD1 2.00000000 secTE 298.4 KDE 8.00 usecDW 19.800 usecRG 2050AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 80SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 18.19Date_ 20180426PROCNO 1EXPNO 2NAME xxy−bf−1b

7 + 1eq NEt3

S45

220 200 180 160 140 120 100 80 60 40 20 0 ppm

184.099

1.574

12.019

23.035

23.650

24.607

25.258

25.633

29.637

29.994

46.810

54.019

77.381

77.700

78.018

113.506

125.128

125.451

131.801

132.746

133.123

133.496

134.887

145.771

187.559




7 + 2eq NEt3

S46

220 200 180 160 140 120 100 80 60 40 20 0 ppm

1.551

12.044

23.015

23.628

24.587

25.239

25.608

29.609

29.962

46.791

53.983

77.380

77.698

78.017

113.488

125.075

125.405

131.839

132.703

133.104

133.436

134.896

145.750

183.962

187.607




7 + 3eq NEt3

S47

220 200 180 160 140 120 100 80 60 40 20 0 ppm

1.538

12.055

23.005

23.616

24.575

25.228

25.593

29.595

29.945

46.785

53.960

77.382

77.700

78.019

113.479

125.070

125.378

131.862

132.682

133.093

133.401

134.902

145.729

183.878

187.632




7 + 4eq NEt3

S48

220 200 180 160 140 120 100 80 60 40 20 0 ppm

1.521

12.033

22.989

23.599

24.559

25.213

25.575

29.577

29.926

30.207

46.764

53.937

77.382

77.701

78.019

101.934

113.465

125.056

125.355

131.865

132.662

133.079

133.374

134.899

145.721

183.822

187.639



TD0 10D11 0.03000000 secD1 2.00000000 secTE 297.7 KDE 8.00 usecDW 19.800 usecRG 2050AQ 1.2976629 secFIDRES 0.385323 HzSWH 25252.525 HzDS 4NS 240SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PADUL 13CINSTRUM spectTime 20.31Date_ 20180426PROCNO 1EXPNO 2NAME xxy−bf−net3−20180426

7 + 5eq NEt3

S49

1-SI222.pdf222.pdf1前半部分.pdf2-si-127AI.pdf2-si-1123-aa2-SI 11232018.8.10 H C7-3-1图谱合并11-dipp-Cl-H2-dipp-Cl-C133-dipp-br-H4-dipp-br-C135-DIPP-CL-CARBENE H6-DIPP-CL-CARBENE C137-DIPP BR CARBENE H8-8DIPP BR CARBENE C139-ASY DIPP BR CARBENE H10-ASY DIPP BR CARBENE C1311-DIPP-I-CARBENE H12-DIPP-I-CARBENE C1313-dipp-Cl-cui-H14-dipp-Cl-cui-C1315-dipp-cl-au-H16-DIPP-CL-AU-C1317-dipp-Br-icu-H18-dipp-Br-icu-C1319-dipp-Br-Au-H20-dipp-Br-Au-C1321-dipp-2I-icu-H22-dipp-2I-icu-C1323-DIPP-I-AU-H-I

zh 13-au with iodide

27-DIPP-I-Ir-Cl-CO28-DIPP-I-Ir-Cl-CO-C13

2I-AU-PF6-H.pdf2I-AU-PF6-c13.pdf

2后半部分.pdf组合6wenj.pdf组合 1.pdf1-DIPP-I-Au-I-H.pdf2-DIPP-I-Au-I-C13.pdf

au-yne-ph.pdfau-yne-phC13.pdf

2019218

Documents

Supporting Information ForSupporting Information For 4-Halo-1,2,3-triazolylidenes: Stable Carbenes Featuring Halogen Bonding Xingyu Xu, Zengyu Zhang, Shiqing Huang, Lei Cao, Wei Liu