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SUPPLEMENTARY INFORMATIONDOI: 10.1038/NCHEM.2502

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Supporting Information for

A motif for reversible nitric oxide interactions in metalloenzymes Shiyu Zhang,a Marie M. Melzer,a S. Nermin Sen,b Nihan Çelebi-Ölçüm,b,* and Timothy H. Warrena,c*

a Department of Chemistry, Georgetown University, Box 571227, Washington, DC 20057, USA b Department of Chemical Engineering, Yeditepe University, Istanbul 34755, Turkey c Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN 47909, USA

Contents General Experimental Details ....................................................................................................................... 2 Preparation of Compounds ........................................................................................................................... 2

Synthesis and Characterization of MesTpCu-SCPh3 (1b) ....................................................................... 2 Synthesis and Characterization of MesTpCu(1-N(O)SCPh3) (2b) ........................................................ 3 Synthesis of iPr2TpCuI(CNArMe2) (3a) ................................................................................................... 4 Synthesis of MesTpCuI(CNArMe2) (3b) ................................................................................................... 5 References for Synthesis and Details .................................................................................................... 5

UV-vis and NMR Spectroscopy Studies Details ........................................................................................... 5 Reaction of iPr2TpCuII-SCPh3 (1a) with NO .......................................................................................... 5 Reaction of iPr2TpCuI(NCMe) with Ph3CSNO ...................................................................................... 6 Reaction of iPr2TpCuI(ONSCPh3) (2a) and 2,6-Dimethylphenyl Isocyanide ........................................ 7 Quantification of iPr2TpCuI(CNAr2,6-Me2) (3a) from Reaction of iPr2TpCu(ONSCPh3) (2a) and CNArMe2 ................................................................................................................................................ 8 Reaction of MesTpCuI(1-N(O)SCPh3) (2b) and 2,6-Dimethylphenyl Isocyanide ................................ 8 Quantification of MesTpCuI(CNAr2,6-Me2) (3b) from Reaction of MesTpCu(1-N(O)SCPh3) (2b) and CNArMe2 .............................................................................................................................................. 10 Interconversion of MesTpCuI(1-N(O)SCPh3) (2b) and MesTpCuII-SCPh3 (1b) .................................... 10 Van’t Hoff Plot of Binding of Ph3CSNO to MesTpCuI(THF) ............................................................... 11 Reaction between MesTpCuI(1-N(O)SCPh3) (2b) and O2 ................................................................... 12 References for Spectroscopy Studies Details ...................................................................................... 13

Cyclic Voltammetry Details ........................................................................................................................ 14 X-Band EPR Details ................................................................................................................................... 16

Formation of MesTpCuI(1-N(O)SCPh3) (2b) from MesTpCuII-SCPh3 (1b) and NO by EPR ............... 18 X-ray Structure Refinement Details ............................................................................................................ 18 Computational Details ................................................................................................................................ 22

Computational Methodology .............................................................................................................. 22 Comparison of B3LYP and B3LYP-D3 geometries and energies ....................................................... 23 References for Calculational Details .................................................................................................. 26 Examination of binding modes for Ph3CSNO at MesTpCuI ................................................................. 26 References for S-nitrosothiol binding modes ...................................................................................... 27 Computed potential energy surface for NO capture/release ................................................................... Illustration of Cu-N(O)SR -backbonding in MesTpCu(1-N(O)SCPh3) isomer .............................. 29 RS…NO interactions in the MesTpCu(NO)(SR) NO/SR isomer ........................................................ 30 Cartesian coordinates of optimized structures .................................................................................... 31 Absolute energies and corrections ...................................................................................................... 52 Complete reference for Gaussian 09 (Reference 44 from manuscript) ............................................... 53

© 2016 Macmillan Publishers Limited. All rights reserved.



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General Experimental Details

All experiments were carried out in a dry nitrogen atmosphere using an MBraun glovebox and/or

standard Schlenk techniques. 4 Å molecular sieves were activated in vacuo at 180 °C for 24 h. Dry

fluorobenzene, dichloromethane, and pentane were purchased from Acros and were stored over activated

4 Å molecular sieves under nitrogen. All deuterated solvents were sparged with nitrogen, dried over

activated 4 Å molecular sieves and stored under nitrogen. 1H, 13C and 15N NMR spectra were recorded on

Varian 400 MHz spectrometer. All NMR spectra were recorded at room temperature unless otherwise

noted. 1H and 13C NMR spectra were indirectly referenced to TMS using residual solvent signals as

internal standards; 15N NMR spectra were referenced to external standard Na15NO2 in D2O (609.5 ppm vs.

NH3). Elemental analyses were performed on a Perkin-Elmer PE2400 microanalyzer in our laboratories,

and UV-Vis spectra were recorded on a Cary 50 spectrophotometer equipped with a Unisoku UnispeKs

cryostat. Na15NO2 was obtained from Cambridge Isotope Laboratories. Nitric oxide gas was obtained

from Praxair and purified by passing through a column of Ascarite (8-20 mesh) purchased from Sigma. In

each experiment involving NO gas, a small amount of NO gas was transferred using a 25 L Hamilton

syringe equipped with a 6’’ needle. The needle tip was first dipped into the solution and with stirring, the

injection of NO gas was made slowly with a rate ca. 10 L/min. MesTpTl,a MesTpCu(THF),b iPr2TpCu(MeCN),c iPr2TpCu-SCPh3 (1a),c Ph3CSNOd and Ph3CS15NOe were prepared based on literature

procedures.

Preparation of Compounds

Synthesis and Characterization of MesTpCu-SCPh3 (1b) A suspension of MesTpTl (0.293 g, 0.379 mmol) and CuCl2 (51.0 mg, 0.379 mmol) in 5 mL CH2Cl2 was

stirred at room temperature for 4 h. The white suspension slowly gave way to a dark red solution. The

resulting solution was filtered over Celite, then added to triethylamine (53.0 L, 0.379 mmol) and

Ph3CSH (0.104 g, 0.379 mmol) at -40 ºC. The solution was kept at -40 ºC for overnight after which dark

blue crystals were formed and were isolated to give 0.227 g (66% yield) of product. EPR (Toluene, 80K):

g1 = 2.164, g2 = 2.053, g3 = 2.053, A1(Cu) = 245 MHz, A2(Cu) = A3(Cu) = 20 MHz, Anal. Calcd. for

C55H55B1Cu1N6S1: C, 72.87; H, 6.12; N, 9.27. Found: C, 72.41; H, 6.06; N, 9.54. Four solutions of MesTpCu-SCPh3 (1b) were made by dissolving crystals in CH2Cl2 in varying concentrations, 0.31 mM,

0.29 mM, 0.28 mM, 0.26 mM to determine value of max and molar absorptivity for 1b (Supplementary

Figure S1). Construction of a Beer’s Law plot (A635nm vs. [1b]) shown in Supplementary Figure S1 gave

max = 635 nm, = 6880 M-1cm-1 for MesTpCu-SCPh3 (1b).




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Supplementary Figure S1. (A) UV-vis spectra of MesTpCu-SCPh3 (1b) in CH2Cl2 at -40 °C (0.31 mM,

0.29 mM, 0.28 mM, 0.26 mM in 1b). (B) Beer’s law plot of 1b to give max = 635 nm with = 6880

M-1cm-1.

Synthesis and Characterization of MesTpCu(1-N(O)SCPh3) (2b) MesTpCu(THF)b (63.0 mg, 90.0 mol) was dissolved in 1 mL fluorobenzene. To the stirring solution of MesTpCu(THF), was added dropwise a solution Ph3CSNO (53.0 mg, 0.174 mmol) in 1 mL fluorobenzene

at -40 ºC. The green solution immediately turned dark red. The resulting solution was kept at -40 ºC for

30 min and filtered over Celite. 4 mL cold pentane was layered on top of the solution at -40 ºC. Dark red

crystals formed after standing at -40 °C overnight which were collected and dried under vacuum to give

50.0 mg (59% yield) of product. 1H NMR (dichloromethane-d2, 300 MHz, -35 °C): 7.77 (d, 3, NCH),

7.27-7.14 (m, 9, ArH), 6.47 (s, 6, p-ArH), 6.25 (d, 3, CH), 1.89 (s, 9, CH3), 1.81 (s, 18, CH3); The 15N-labeled MesTpCu(1-15N(O)SCPh3) was prepared with Ph3CS15NO using similar procedure. 15N NMR

(dichloromethane-d2, 40.5 MHz, -35 °C) 566.1 ppm vs. NH3 (Supplementary Figure S2A); IR (ATR, ca.

-40 °C) 1424 cm-1 (NO stretch) which shifts to 1399 cm-1 with Ph3CS15NO (Supplementary Figure S2C).

Supplementary Figure S2. (A) 15N NMR spectra (40.5 MHz, dichloromethane-d2) of Ph3CS15NO at

-57 °C with signals at 843.8 (anti) and 754.8 (syn) ppm (top/blue), Ph3CS15NO at RT with averaged

signal at 807.1 ppm (middle/green) and MesTpCu(1-N(O)SCPh3) (2b) at -35 °C with signal at 566.1

ppm (bottom/red); (B) IR spectra of Ph3CSNO and Ph3CS15NO with (NO) at 1487 and 1459 cm-1; (C) IR

spectra of MesTpCu(1-N(O)SCPh3) and MesTpCu(1-15N(O)SCPh3) with (NO) at 1424 and 1399 cm-1.




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In situ UV-Vis spectroscopy of the reaction of MesTpCuI(THF) with Ph3CSNO was conducted at -40 °C to

determine value of max and molar absorptivity for pure 2b (Supplementary Figure S3A). MesTpCuI(THF)

(2.70 mL, 0.556 mM, 1.50 μmol, CH2Cl2) was placed in a quartz cuvette with a rubber septum in an inert

atmosphere at -40 °C. Ten equivalents of Ph3CSNO (0.30 mL, 50.0 mM, 15 μmol, CH2Cl2) was syringed

into the cuvette to bring the final concentration of MesTpCuI(THF) to 0.50 mM. UV-vis spectra were taken

every 30 s. The absorbance at 512 nm corresponding to MesTpCuI(1-N(O)SCPh3) (2b) reached a

maximum after 15 min. Five other solutions of MesTpCuI(1-N(O)SCPh3) (2b) were made in varying

concentrations, 0.43 mM, 0.38 mM, 0.33 mM, 0.30 mM and 0.27 mM by adding CH2Cl2 and diluting the

initial MesTpCuI(THF) solution. Construction of a Beer’s Law plot (A512nm vs. [2b]) shown in

Supplementary Figure S3B gave max = 512 nm with = 4200 M-1cm-1 for MesTpCuI(1-N(O)SCPh3) (2b).

Supplementary Figure S3. (A) UV-vis spectra of MesTpCuI(THF) and 10 equiv Ph3CSNO at -40 °C at

different concentrations (0.5 mM, 0.43 mM, 0.38 mM, 0.33 mM, 0.30 mM, 0.27 mM). (B) Beer’s law

plot of 2b to give = 422 nm with = 2920 M-1cm-1 (orange) and max = 512 nm with = 4200 M-1cm-1

(blue).

Synthesis of iPr2TpCuI(CNArMe2) (3a) iPr2TpCuI(NCMe) (0.105 g, 0.184 mmol) was dissolved in 1 mL CH2Cl2

and added to 2,6-dimethylphenyl

isocyanide (26.0 mg, 0.198 mmol) in 1 mL CH2Cl2. The reaction was allowed to stand at room

temperature for 5 min. The resulting solution was layered with 2 mL pentane. Colorless crystals formed

overnight at -40 ºC. The crystals were collected and dried under reduced pressure to give 59.0 mg product

(49% yield). 1H NMR (CD2Cl2, 400 MHz): δ 7.26 (t, 1, p-ArH), 7.18 (d, 2, m-ArH), 5.82 (s, 3, pzH), 3.74

(m, 3, CH(CH3)2), 3.27 (m, 3, CHMe2), 2.49 (s, 6, ArCH3), 1.25 (dd, 36, (CH3)2CH); 13C{1H} NMR

(CD2Cl2, 100 MHz): δ 158.2, 154.9, 135.3, 128.7, 128.3, 110.47, 96.6, 28.5, 26.5, 24.0, 23.5, 19.0. IR:

CN (2109 cm-1). Anal. Calcd. for C36H55B1Cu1N7: C, 65.49; H, 8.40; N, 14.85. Found: C, 65.28; H, 8.43;

N, 14.95.




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Synthesis of MesTpCuI(CNArMe2) (3b) MesTpCuI(THF) (41.0 mg, 58.0 mol) was dissolved in 1 mL CH2Cl2

and added to 2,6-dimethylphenyl

isocyanide (8.0 mg, 61 mol) in 1 mL CH2Cl2. The reaction was allowed to stand at RT for 5 min. The

resulting solution was layered with 2 mL pentane. A white powder formed after standing overnight at -40

ºC was collected and dried under reduced pressure to give 22.0 mg product (50% yield). 1H NMR

(CD2Cl2, 400 MHz): δ 7.78 (d, 3, NCH), 7.05 (t, 1, p-ArH), 6.93 (d, 2, m-ArH), 6.66 (s, 6, m-ArH), 6.03

(d, 3, NCCH), 1.97 (s, 9, p-ArCH3), 1.95 (s, 18, o-ArCH3), 1.66 (s, 6, o-ArCH3); 13C{1H} NMR (CD2Cl2,

100 MHz): δ 151.05, 137.85, 137.33, 135.00, 134.47, 132.01, 128,08, 127.86, 127.54, 104.80, 20.95,

20.84, 18.24. IR: CN (2123 cm-1). Anal. Calcd. for C45H49B1Cu1N7: C, 70.90; H, 6.48; N, 12.86. Found: C,

70.63; H, 6.35; N, 12.76.

References for Synthesis and Details

(a) Rheingold, A. L.; White, C. B.; Trofimenko, S., Inorg. Chem. 1993, 32, 3471-7.

(b) Schneider, J. L.; Carrier, S. M.; Ruggiero, C. E.; Young, V. G.; Tolman, W. B., J. Am. Chem. Soc. 1998,

120, 11408-11418.

(c) Zhang, S.; Çelebi-Ölçüm, N.; Melzer, M. M.; Houk, K. N.; Warren, T. H., J. Am. Chem. Soc. 2013,

135, 16746-16749.

(d) Melzer, M. M.; Mossin, S.; Cardenas, A. J. P.; Williams, K. D.; Zhang, S.; Meyer, K.; Warren, T. H.,

Inorg. Chem. 2012, 51, 8658–8660.

(e) Arulsamy, N.; Bohle, D. S.; Butt, J. A.; Irvine, G. J.; Jordan, P. A.; Sagan, E., J. Am. Chem. Soc. 1999,

121, 7115-7123.

UV-vis and NMR Spectroscopy Studies Details

Reaction of iPr2TpCuII-SCPh3 (1a) with NO iPr2TpCuII-SCPh3 (1a) (3.00 mL, 0.310 mM, 0.930 μmol, CH2Cl2) was placed in a quartz cuvette with a

rubber septum in an inert atmosphere. NO gas (21 L @ 1 atm @ RT, 0.94 μmol) was syringed into the

cuvette at -70 ºC. The peak at 630 nm corresponding to iPr2TpCuII-SCPh3 decreased over time along with

isosbestic formation of new peaks at 445 nm (ca. 3600 M-1cm-1) and 570 nm (ca. 3200 M-1cm-1)1

(Supplementary Figure S4). Additional changes in the UV-vis spectrum were not noticed after 15 min,

indicating that equilibrium was reached.

1 Assuming quantitative conversion of 1a to 2a.




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Supplementary Figure S4. Reaction of 1a (0.31 mM) and 1 equiv. NOgas to give 2a at -70 ºC in CH2Cl2 (3 min / scan). Reaction of iPr2TpCuI(NCMe) with Ph3CSNO iPr2TpCuI(NCMe) (2.70 mL, 0.333 mM in CH2Cl2, 0.900 μmol) was placed in a quartz cuvette with a

rubber septum in an inert atmosphere at -70 ºC in CH2Cl2. Ph3CSNO (0.30 mL, 3.00 mM in CH2Cl2, 0.90

μmol) was syringed into the cuvette to bring the solution to a final volume of 3.0 mL, 0.30 mM in each

component. The absorbances at 445 nm and 570 nm which correspond to iPr2TpCuI(ONSCPh3) (2a) reach

their maxima after 15 min (A570 = 0.569, ca. 59% spectroscopy yield) (Supplementary Figure S5A).

Warming the resulting solution of 2a to -60 ºC results in decrease of 445 and 570 nm peaks over time

along with partial formation of 1a (max = 625 nm, ≈ 6600 M-1cm-1) in ca. 14% yield (A625 = 0.276) with

respect to iPr2TpCuI(NCMe) initial concentration (Supplementary Figure S5B). Attempts to further follow

this decomposition reaction were unsuccessful, likely due to the known thermal instability of iPr2TpCu-SCPh3 which is subject to Ph3C• radical loss to form {iPr2TpCu}2(-2:2-S2).f

The 15N-labeled iPr2TpCu(O15NSCPh3) was prepared with Ph3CS15NO in CD2Cl2 at -78 °C for 15N

NMR spectroscopic analysis (Supplementary Figure S5). 15N NMR (dichloromethane-d2, 40.5 MHz,

-50 °C) 558.7 ppm vs. NH3 (Supplementary Figure S5C).

Supplementary Figure S5. UV-vis spectra of (A) reaction of iPr2TpCuI(NCMe) (0.30 mM) and Ph3CSNO

to give 2a at -70 ºC in CH2Cl2 and (B) warming of CH2Cl2 solution of 2a (0.18 mM) to give partial

formation of 1a at -60 °C in CH2Cl2 (1 min / scan). (C) 15N NMR spectrum of intermediate iPr2TpCuI(O15NSCPh3) (2a) at -50 °C with signal at 558.7 ppm vs. NH3

2a




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Reaction of iPr2TpCuI(ONSCPh3) (2a) and 2,6-Dimethylphenyl Isocyanide

NOPh3CSNOiPr2TpCuII-SCPh3

iPr2TpCuI(ONSCPh3)1a -70 oC -70 oC2a

CNAr2,6-Me

iPr2TpCuI(CNAr2,6-Me)

iPr2TpCuII-SCPh3 (1a) (3.00 mL, 0.500 mM in CH2Cl2, 1.50 μmol) was placed in a quartz cuvette with a

rubber septum in an inert atmosphere at -70 °C. NO gas (34 L @ 1 atm @ RT, 1.5 μmol) was syringed

into the cuvette. UV-vis spectra were taken every 30 s. The absorbance at 625 nm corresponding to iPr2TpCuII-SCPh3 (1a) decreases, and a new peak at 570 nm grows in corresponding to iPr2TpCuI(ONSCPh3)

(2a). Two equiv. 2,6-dimethylphenyl isocyanide (0.60 mL, 5.00 mM, 3.0 μmol, CH2Cl2) was then added

into the solution. The color of the solution immediately changed from dark red to light green. The new

absorbance at 605 nm is attributed to Ph3CSNO (Supplementary Figure S6).a

Supplementary Figure S6. UV-vis spectra of the reaction of iPr2TpCuI(ONSCPh3) (1a) (0.42 mM) and 2

equiv. 2,6-dimethylphenyl isocyanide at -70 °C in CH2Cl2. 2a was generated in situ from iPr2TpCuII-SCPh3

(1a) (0.500 mM) and one equiv. NOgas. Spectrum on the right shows weak absorbance at = 605 nm due

to Ph3CSNO.

Ph3CSNOPh3CSNO

iPr2TpCuI(NCMe) iPr2TpCuI(ONSCPh3)-MeCN-70 oC

-70 oC2a

CNAr2,6-MeiPr2TpCuI(CNAr2,6-Me)

3a

iPr2TpCuI(NCMe) (2.70 mL, 0.278 mM in CH2Cl2, 0.750 μmol) was placed in a quartz cuvette with a

rubber septum in an inert atmosphere at -70 °C. One equivalent of Ph3CSNO (0.30 mL, 2.50 mM in

CH2Cl2, 0.75 μmol) was syringed into the cuvette. UV-vis spectra were taken every 30 s. The absorbance

at 570 nm corresponding to iPr2TpCuI(ONSCPh3) (1a) reached a maximum after 60 min (A = 0.414, ca.

52% spectroscopic yield). Two equiv. 2,6-dimethylphenyl isocyanide (0.30 mL, 5.00 mM in CH2Cl2, 1.5

μmol) was then added into the solution. The color of the solution immediately changed from dark red to

light green with absorbance at 605 nm attributed to Ph3CSNO (Supplementary Figure S7).a




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Supplementary Figure S7. UV-vis spectrum of the reaction of iPr2TpCuI(ONSCPh3) (2a) (0.13 mM) and

2 equiv. 2,6-dimethylphenyl isocyanide at -70 °C in CH2Cl2. 2a was generated in situ from iPr2TpCuI(NCMe) and Ph3CSNO.

Quantification of iPr2TpCuI(CNAr2,6-Me) (3a) from Reaction of iPr2TpCu(ONSCPh3) (2a) and CNArMe2 iPr2TpCuI(NCMe) (27.0 mg, 52.0 mol) and the internal standard ferrocene (10.0 mg, 52.0 mol) were

mixed together in 1 mL CD2Cl2. An initial 1H NMR spectrum was taken to verify the actual ratio of iPr2TpCuI(NCMe):Cp2Fe. This solution was added to Ph3CSNO (16.0 mg, 52.0 mol) solid at -70 ºC. The

mixture was allowed to sit at -70 ºC for 5 min upon which the color changed from green to dark red. The

solution was added into one equivalent of 2,6-dimethylphenyl isocyanide (7.0 mg, 52 mol). The color of

the solution immediately changed from dark red to yellowish green. A 1H NMR spectrum was taken of

the solution. iPr2TpCuI(CNArMe2) (3a) (80 % yield) and Ph3CSNO were found to be the sole products by 1H NMR.

Reaction of MesTpCuI(1-N(O)SCPh3) (2b) and 2,6-Dimethylphenyl Isocyanide

NOMesTpCuII-SCPh3

MesTpCuI(1-N(O)SCPh3)1b -70 oC -70 oC2b

CNAr2,6-Me

MesTpCuI(CNAr2,6-Me) + ONSCPh3

MesTpCuII-SCPh3 (1b) (3.00 mL, 0.500 mM in CH2Cl2, 1.50 μmol) was placed in a quartz cuvette with a

rubber septum in an inert atmosphere at -70 °C. NO gas (34 L @ 1 atm @ RT, 1.5 μmol) was syringed

into the cuvette. UV-vis spectra were taken every 30 s. The absorbance at 635 nm corresponding to MesTpCuII-SCPh3 (1b) decreases and a new peak at 512 nm grows in corresponding to MesTpCuI(1-N(O)SCPh3) (2b) in quantitative spectroscopic yield (A512 = 2.45). 2,6-Dimethylphenyl

isocyanide (0.60 mL, 5.00 mM in CH2Cl2, 3.0 μmol) was then added to the solution. The color of the

solution immediately changed from dark red to light green giving a new absorbance at 605 nm attributed

to Ph3CSNO (Supplementary Figure S8).g




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Supplementary Figure S8. UV-vis spectra of the reaction of MesTpCuI(1-N(O)SCPh3) (2b) (0.50 mM)

and 2 equiv. 2,6-dimethylphenyl isocyanide at -70 °C in CH2Cl2. 2b was generated in situ from MesTpCuII-SCPh3 (1b) and NO. The spectrum on the right corresponds to the weak absorbance of free

Ph3CSNO at = 605 nm.

Ph3CSNOPh3CSNO

MesTpCuI(THF) MesTpCuI(1-N(O)SCPh3)- THF-40 oC

-40 oC2b

CNAr2,6-Me

MesTpCuI(CNAr2,6-Me) +3b

MesTpCuI(THF) (2.70 mL, 0.556 mM in CH2Cl2, 1.50 μmol) was placed in a quartz cuvette with a rubber

septa in an inert atmosphere at -70 °C. Ph3CSNO (0.30 mL, 5.00 mM in CH2Cl2, 1.5 μmol) was syringed

into the cuvette. UV-vis spectra were taken every 30 s. The absorbance at 512 nm corresponding to MesTpCuI(1-N(O)SCPh3) (2b) reached a maximum after 60 min (A512nm = 0.92, 44% spectroscopic yield).

2,6-Dimethylphenyl isocyanide (0.60 mL, 5.00 mM, 3.0 μmol, CH2Cl2) was then added to the solution.

The color of the solution immediately changed from dark red to light green with absorbance at 605 nm

attributed to Ph3CSNO (Supplementary Figure S9).

Supplementary Figure S9. UV-vis spectra of the reaction of MesTpCuI(1-N(O)SCPh3) (2b) (2.2 mM)

and 2 equiv. 2,6-dimethylphenyl isocyanide at -70 °C in CH2Cl2. 2b was generated in situ from MesTpCuI(THF) and Ph3CSNO at -70 °C in CH2Cl2. The lower green spectrum shows a residual feature

near 600 nm due to free Ph3CSNO.




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Quantification of MesTpCuI(CNAr2,6-Me) (3b) from Reaction of MesTpCu(1-N(O)SCPh3) (2b) and CNArMe2 MesTpCuI(THF) (17.0 mg, 24.2 mol) and the internal standard ferrocene (6.0 mg, 32 mol) were mixed

together in 1 mL of CD2Cl2. An initial 1H NMR spectrum was taken to determine the actual ratio of MesTpCuI(THF):Cp2Fe. This solution was added to Ph3CSNO (8.0 mg, 26 mol) solid at -40 ºC. The

mixture was allowed to stand at -40 ºC for 5 minutes upon which the color changed from green to dark

red. The solution was added into 2, 6-dimethylphenyl isocyanide (4.0 mg, 31 mol). The color of the

solution immediately changed from dark red to yellowish green. A 1H NMR spectrum was taken of the

solution indicating the quantitative formation of MesTpCuI(CNArMe2) (3b) and Ph3CSNO.

Interconversion of MesTpCuI(1-N(O)SCPh3) (2b) and MesTpCuII-SCPh3 (1b) Loss of NO MesTpCu(1-N(O)SCPh3) (2b) was prepared in situ from the reaction of MesTpCuI(THF) and

Ph3CSNO (A512nm = 0.363, 70% spectroscopic yield) by placing MesTpCuI(THF) (2.70 mL, 0.139 mM,

0.375 μmol) in a quartz cuvette with a rubber septum in an inert atmosphere at 0 °C followed by addition

of Ph3CSNO (0.30 mL, 1.25 mM in CH2Cl2, 0.38 μmol) by syringe to bring the solution to a final volume

of 3 mL, 0.125 mM for both MesTpCuI(THF) and Ph3CSNO. After mixing, the reaction solution was

purged with a stream of N2. UV-vis spectra were taken every 60 s. The absorbances at 422 nm and 512

nm which correspond to 2b decrease over time and a new peak at 635 nm that corresponds to 1b grows in

(A635nm = 0.802, 93% spectroscopic yield) (Supplementary Figure S10). Additional changes in the UV-vis

spectrum were not noticed after 60 min.

Supplementary Figure S10. UV-vis spectra indicating the conversion of 2b (0.0875 mM) to 1b at 0 °C

in CH2Cl2.




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Capture of NO The same reaction mixture described above was cooled to -80 °C and 1.1 equiv NOgas (9.0

L @ 1atm @ RT, 0.40 μmol) was syringed into the cuvette. UV-vis spectra were taken every 60 s for 12

min. The absorbance at = 635 nm which corresponds to MesTpCuII-SCPh3 decreased over time and

absorbances at 422 nm and 512 nm that correspond to MesTpCuI(1-N(O)SCPh3) grow in during the scans

(A512nm = 0.367, 70% yield) (Supplementary Figure S11).

Supplementary Figure S11. UV-vis spectra indicating the conversion of MesTpCuII-SCPh3 (1b)

(generated by loss of NO) to MesTpCuI(1-N(O)SCPh3) (2b) via addition of NO to in situ formed 1b at

-80 °C in CH2Cl2.

Van’t Hoff Plot of Binding of Ph3CSNO to MesTpCuI(THF) MesTpCuI(THF) (2.70 mL, 0.560 mM in CH2Cl2, 1.50 μmol) was placed in a quartz cuvette with a rubber

septa in an inert atmosphere at -50 °C. Ph3CSNO (0.30 mL, 5.00 mM, 1.5 μmol, CH2Cl2) by syringe to

bring the solution to a final volume of 3.00 mL corresponding to concentrations of 0.50 mM for both MesTpCuI(THF) and Ph3CSNO. UV-vis spectra were taken every 30 s. The absorbance at 512 nm

corresponding to 2b reached a maximum after 1 h. The reaction was cooled down to -60 °C and

maintained at this until equilibrium was established (ca. 1 h). The same reaction mixture was cooled

down to -70 °C and -80 °C with UV-vis spectra taken at each temperature after equilibrium was

established (ca. 2 h). At lower temperatures, more 2b was observed (Supplementary Figure S12A).

Construction of a van’t Hoff plot (ln(Keq) vs. 1/T) shown in Supplementary Figure S12B gave Hr =

-0.82(2) kcal/mol; Sr = -2.7(1) e.u for the reaction shown in Supplementary Scheme S1. Addition of

excess THF did not alter the position of equilibrium, suggesting that instead MesTpCu exists as a solvent

bound species MesTpCu(solvent) at these concentrations.

MesTpCu + Ph3CSNO2b

MesTpCu(1-N(O)SCPh 3)CH2Cl2

Keq =[2b]eq

[Cu]eq [Ph3CSNO]eq

Supplementary Scheme S1. Equilibrium between MesTpCu and Ph3CSNO to give MesTpCuI(1-N(O)SCPh3) (2b).




S12

Supplementary Table S2. Concentration of reactants and products for van’t Hoff plot in Supplementary

Figure S12.

Supplementary Figure S12. (A) UV-vis spectra of the reaction of MesTpCuI in CH2Cl2 (initial

concentration = 0.50 mM) with 1 equiv Ph3CSNO to give MesTpCu(1-N(O)SCPh3) (2b). The strong band

of 2b at max = 512 nm was monitored and quantified by UV-vis spectroscopy to calculate [2b] as well as

the equilibrium constant Keq in Supplementary Scheme S1. (B) van’t Hoff plot of MesTpCuI with

Ph3CSNO to give 2b; Hr = -0.82(2) kcal/mol; Sr = -2.7 (1) e.u.

Reaction between MesTpCuI(1-N(O)SCPh3) (2b) and O2 A solution of MesTpCuI(1-N(O)SCPh3) (2b) was generated by addition of a solution of MesTpCuI(THF) to

a solution of Ph3CSNO as follows: Ph3CSNO (2.50 mL, 5.00 mM, 12.5 μmol, CH2Cl2) was placed in a

quartz cuvette with a rubber septum in an inert atmosphere at -40 °C. MesTpCuI(THF) (0.50 mL, 5.00 mM

in CH2Cl2, 2.50 μmol) by syringe to bring the solution to a final volume of 3.00 mL corresponding to

concentrations of 0.83 mM for MesTpCuI(THF) and 4.17 mM for Ph3CSNO. UV-vis spectra were taken

every 6 mins. The absorbance at 512 nm which corresponds to 2b reached a maximum after 4 hours. The

reaction was then exposed to 1 atm O2 at -40 °C by addition of an O2 balloon to the cuvette. The

absorbance at = 512 nm which corresponds to MesTpCuI(1-N(O)SCPh3) (2b) MesTpCuII-SCPh3

decreased and the absorbance at 635 nm corresponding to MesTpCuII-SCPh3 grew in slowly over 2 h

(Supplementary Figure S13). No decomposition of MesTpCuI(1-N(O)SCPh3) (2b) was observed in the

absence of O2 at -40 °C in CH2Cl2 for at least 3 h.

Temperature MesTpCu(THF) concentration

Ph3CSNO concentration

2b A512nm

2b

concentration

Keq

-50 °C 0.327 mM 0.327 mM 0.724 0.173 mM 1.61 -60 °C 0.319 mM 0.319 mM 0.757 0.181 mM 1.77 -70 °C 0.311 mM 0.311 mM 0.791 0.189 mM 1.94 -80 °C 0.303 mM 0.303 mM 0.826 0.197 mM 2.15




S13

Supplementary Figure S13. UV-vis spectra indicating slow conversion of MesTpCuI(1-N(O)SCPh3)

(generated in situ from MesTpCuI(THF) and 5 equiv. Ph3CSNO) (2b) to MesTpCuII-SCPh3 (1b) under 1 atm

O2 at -40 °C in CH2Cl2 over 2 h (6 min / scan).

References for Spectroscopy Studies Details

(f) Fujisawa, K.; Moro-oka, Y.; Kitajima, N., J. Chem. Soc., Chem. Commun. 1994, 623-624.

(g) Arulsamy, N.; Bohle, D. S.; Butt, J. A.; Irvine, G. J.; Jordan, P. A.; Sagan, E., J. Am. Chem. Soc.

1999, 121, 7115-7123.




S14

Cyclic Voltammetry Details

Cyclic voltammetry measurements were done at room temperature under an N2 atmosphere in a glovebox

using BASi Epsilon Electrochemistry System with three electrodes (Pseudo-reference: Ag wire; Working:

glassy carbon; Auxillary: platinum). The [Bu4N]PF6 electrolyte was recrystallized from ethanol and

thoroughly dried prior to use.

Supplementary Figure S14. Cyclic voltammogram of iPr2TpCuII-SCPh3 (1a) and ferrocene standards in

CH2Cl2 at 4.0 mM and 2.0 mM concentrations, respectively. Horizontal axis in volts. Electrolyte: 0.20 M

NBu4PF6 in dichloromethane. Scan rate 50 mV/s. E1/2 (1a) = -0.91 V vs. Fc which corresponds to E1/2 =

-0.21 V vs. NHE.h

Supplementary Figure S15. Cyclic voltammogram of MesTpCuII-SCPh3 (1b) and ferrocene standards in

CH2Cl2 at 4.0 mM and 2.0 mM concentrations, respectively. Horizontal axis in volts. Electrolyte: 0.20 M

NBu4PF6 in dichloromethane. Scan rate 50 mV/s. E1/2 = -0.62 V vs. Fc. which corresponds to E1/2 = 0.08

V vs. NHE.h




S15

Supplementary Figure S16. Cyclic voltammogram of Ph3CSNO and ferrocene standards in CH2Cl2 at

4.0 mM and 1.0 mM concentrations, respectively. Horizontal axis in volts. Electrolyte: 0.20 M NBu4PF6

in dichloromethane. Scan rate 50 mV/s. Ered = -1.44 V and -1.95 V vs. Fc which corresponds to Ered =

-0.74 V and -1.25 V vs. NHE.h

Supplementary Figure S17. Cyclic voltammogram of MesTpCuI(1-N(O)SCPh3) (2b) and ferrocene

standards in DCM at 2.0 mM and 1.0 mM concentrations, respectively. Horizontal axis in volts.

Electrolyte: 0.20 M NBu4PF6 in dichloromethane. Scan rate 50 mV/s. Ered = -1.44 V and -1.95 V vs. Fc;

Eox = 0.49 V vs. Fc which corresponds to Ered = -0.74 V and -1.25 V vs. NHE; Eox = +1.19 V vs. NHE.h

General Reference for Cyclic Voltammetry Details:

(h) Connelly, N. G.; Geiger, W. E. Chem. Rev. 1996, 96, 877-910.




S16

X-Band EPR Details

EPR measurements were performed in quartz tubes. Spectral simulation was performed using the

program QCMP 136 by Prof. Dr. Frank Neese from the Quantum Chemistry Program Exchange as used

by Neese et al. in J. Am. Chem. Soc. 1996, 118, 8692-8699. The fittings were performed by the “chi by

eye” approach. EPR spectra of 1a was recorded on a Bruker EMX EPR X-band spectrometer with

small-volume power saturation and dual mode cavities. EPR spectra of 1b were recorded on a JEOL

continuous wave spectrometer JES-FA200 equipped with an X-band Gunn oscillator bridge, a cylindrical

mode cavity, and a liquid nitrogen cryostat. For all samples, a modulation frequency of 100 kHz and a

time constant of 0.03 s were employed.

Supplementary Figure S18. X-band EPR spectrum and simulation for iPr2TpCuII-SCPh3 (1a) (frozen CH2Cl2 at 130 K, 9.429438 GHz, ModWidth = 0.1 mT, Power = 20 mW. Simulation was performed using a 1 Cu model: g1 = 2.220, g2 = 2.055, g3 = 2.055 with A1(Cu) = 220 MHz, A2(Cu) = A3(Cu) = 55 MHz,. Gaussian lineshape, line broadening W1 = 33 mT, W2 = 35 mT, W3 = 35 mT.




S17

Supplementary Figure S19. X-band EPR spectrum and simulation for MesTpCuII-SCPh3 (1b) (frozen toluene glass at 80 K, 8.917452 GHz, ModWidth = 0.1 mT, Power = 0.998 mW). Simulation was performed using a 1 Cu model: g1 = 2.164, g2 = 2.053, g1 = 2.053 with A1(Cu) = 245 MHz, A2(Cu) = A3(Cu) = 20 MHz,. Gaussian lineshape, line broadening W1 = 28 mT, W2 = 27 mT, W3 = 27 mT.

Supplementary Figure S20. X-band EPR spectrum and simulation for MesTpCuII-SCPh3 (1b) (4 mM toluene solution at RT, 8.913065 GHz, ModWidth = 0.02 mT, Power = 0.998 mW). Simulation was performed using a 1 Cu model: giso = 2.090 with Aiso(Cu) = 79 MHz. Gaussian lineshape, line broadening Wiso = 17 mT, C2X = C2Y = C2Z =6.5, EX = EY = EZ = 0.005.




S18

Formation of MesTpCuI(1-N(O)SCPh3) (2b) from MesTpCuII-SCPh3 (1b) and NO by EPR MesTpCuII-SCPh3 (1b) (0.500 mL, 5.00 mM CH2Cl2, 2.50 μmol) was placed in a quartz EPR tube in an

inert atmosphere at -80 °C. ½ equiv. NO gas (30 L @ 1atm @ RT, 1.3 μmol) was syringed into the EPR

tube. After mixing, the reaction solution was frozen in liquid nitrogen and an EPR spectrum was taken at

80 K. An EPR spectrum of the reaction of 1b with 1 equiv NO (60 L @ 1atm @ RT, 2.7 μmol) was

obtained with a similar procedure. The EPR signal corresponding to 1b decreases with increasing amount

of NO, indicating formation of diamagnetic compound 2b.

Supplementary Figure S21. Frozen glass X-band EPR specta of MesTpCuII-SCPh3 (1b) (blue) (initially 5

mM in CH2Cl2), MesTpCuII-SCPh3 (1b) with ½ equiv NO (purple), and MesTpCuII-SCPh3 (1b) with 1 equiv

of NO (red). 8.917404 GHz, ModWidth = 0.1 mT, Power = 0.998 mW. X-ray Structure Refinement Details

Single crystals of each compound MesTpCu-SCPh3 (1b) (CCDC 1401110), MesTpCu(1-N(O)SCPh3) (2b)

(CCDC 1401111) and iPr2TpCuI(CNAr2,6-Me2) (3a) (CCDC 1401112) were mounted under mineral oil on

glass fibers and immediately placed in a cold nitrogen stream at 100(2) K on a Bruker SMART CCD

system. Either full spheres (triclinic) or hemispheres (monoclinic or higher) of data were collected (0.3

or 0.5-scans; 2θ max = 56 ; monochromatic Mo Ka radiation, λ = 0.7107 Å) depending on the crystal

system and integrated with the Bruker SAINT program. Structure solutions were performed using the

SHELXTL/PC suitei and XSEED.j Intensities were corrected for Lorentz and polarization effects and an

empirical absorption correction was applied using Blessing’s method as incorporated into the program

SADABS.k, l Non-hydrogen atoms were refined with anisotropic thermal parameters and hydrogen atoms

were included in idealized positions. Structures for 1b, 2b and 3a were rendered with POV-Ray in

XSEED using 50% probability ellipsoids. A CheckCIF B-level alert present in the X-ray structure of 2b

results from a short C-C distance in one of two fluorobenzene solvent molecules in the unit cell. Since

this B-level alert corresponded to a solvent molecule, no additional restraints were added to the model.




S19

References for X-ray Structure Refinement Details

(i) SHELXTL-PC, Vers. 5.10; 1998, Bruker-Analytical X-ray Services, Madison, WI; G. M. Sheldrick,

SHELX-97, Universität Göttingen, Göttingen, Germany.

(j) L. Barbour, XSEED, 1999.

(k) SADABS; G. M. Sheldrick, 1996, based on the method described in R. H. Blessing, Acta Crystallogr.,

Sect. A, 1995, 51, 33.

(l) Spek, A. L. Acta Crystallogr. 1990, A46, C-34.

Supplementary Figure S22. X-ray crystal structure of MesTpCuII-SCPh3 (1b) (all H atoms and 1 pentane

molecule omitted; thermal ellipsoids represented at the 50% probability level). Selected bond distances (Å)

and angles (°): Cu1-N1 1.997(3), Cu1-N3 2.009(3), Cu1-N5 2.240(3), Cu1-S1 2.1034(11), S1-C37

1.865(4), Cu-S1-C37 131.40(12), N1-Cu1-N3 91.97(12), N3-Cu-N5 89.27(12), N1-Cu1-N5 90.45(12),

N1-Cu1-S1 138.14(9), N3-Cu1-S1 129.54(10), N5-Cu1-S1 94.60(8), (angles about Cu1: N1, N3, and S1)

= 359.65°.




S20

Supplementary Figure S23. X-ray crystal structure of MesTpCuI(1-N(O)SCPh3) (2b) (all H atoms and

two fluorobenzene molecules omitted; thermal ellipsoids represented at the 50% probability level).

Selected bond distances (Å) and angles (°): Cu1-N1 2.044(4), Cu1-N3 2.014(4), Cu1-N5 2.133(4),

Cu1-N7 1.893(4), Cu1…S1 3.044(2), N7-O1 1.206(5), N7-S1 1.755(4), S1-C37 1.884(5) Cu1-N7-S1

113.1(2), Cu1-N7-O1 126.7(3), O1-N7-S1 120.2(3), N1-Cu1-N3 94.75(15), N3-Cu-N5 89.95(14),

N1-Cu1-N5 88.94(15), N1-Cu1-N7 127.88(16), N3-Cu1-N7 126.56(16), N5-Cu1-N7 117.55(16), sum of

angles around N7 = 360.0. Dihedral angles N5-Cu1-N7-O = 8.2; O-N7-S1-C37 = -14.7.




S21

Supplementary Figure S24. X-ray crystal structure of iPr2TpCuI(CNAr2,6-Me2) (all H atoms and two

dichloromethane molecules omitted; thermal ellipsoids represented at the 50% probability level). Selected

bond distances (Å) and angles (°): Cu1-C28 1.813(4), Cu1-N1 2.062(3), Cu1-N3 2.052(3), Cu1-N5

2.079(3), C28-N7 1.165(5), Cu1-C28-N7 176.7(3), N1-Cu1-N3 90.73(11), N3-Cu-N5 89.87(11),

N1-Cu1-N5 91.12(11), N1-Cu1-C28 121.75(13), N3-Cu1-C28 130.70(13), N5-Cu1-C28 121.90(13).




S22

Computational Details

Computational Methodology All calculations were performed with Gaussian 09 (Reference 44 from manuscript)m in the gas phase.

Geometry optimizations were carried out both at the (U)B3LYP/6-311G(d) and (U)B3LYP-D3/6-311G(d)

levels. A comparison of these geometries with the experimental crystal structures are given in a later

section of the supplementary material. The stationary points were characterized using harmonic

vibrational frequencies.

The molecular electronic energies E were computed using dispersion corrected DFT given by equation:

E = EDFT + Edisp

where EDFT is the (all-electron) KS-DFT SCF energy for B3LYP and Edisp is the standard atom pair-wise

London dispersion energy from D3 theory.n The corrections from energy to enthalpy and free energy also

including zero-point vibrational energies, calculated using the harmonic oscillator approximation at

298.15 K, were added to the molecular electronic energies.

All syn- and anti- configurations were considered in the calculations.

All orbital contour plots were rendered by the program “Lumo” by Matthew T. Kieber-Emmons.o




S23

Comparison of B3LYP and B3LYP-D3 geometries and energies

Supplementary Figure S25. Optimized geometry of MesTpCu-N(O)SCPh3-syn using (a)

B3LYP/6-311G(d), (b) B3LYP-D3/6-311G(d), and the (c) X-ray structure. Hydrogen atoms are omitted

for clarity.

(a) (b)

(c)

τ (Cu-N-N1-N2) = 22.1° τ (Cu-N-N1-N2) = 26.6 °

τ (Cu-N-N1-N2) = 25.5°




S24

Supplementary Figure S26. Optimized geometry of iPr2TpCu-SCPh3 using (a) B3LYP/6-311G(d), (b)

B3LYP-D3/6-311G(d), and the (c) X-ray structure.p Hydrogen atoms are omitted for clarity.

(a) (b)

(c)

τ (Cu-S-N1-N2) = 12.6° τ (Cu-S-N1-N2) = 14.7°

τ (Cu-S-N1-N2) = 17.1°




S25

Supplementary Figure S27. Optimized geometry of the MesTpCu-SCPh3 using (a) B3LYP/6-311G(d), (b)

B3LYP-D3/6-311G(d), and the (c) X-ray structure. Hydrogen atoms are omitted for clarity.

(a)

τ (Cu-S-N1-N2) = 1.2°

(b)

τ (Cu-S-N1-N2) = 0.1°

(c)

τ (Cu-S-N1-N2) = 4.3°




S26

References for Calculational Details (m) M. J. Frisch, et al. Gaussian 09, Revision C.01, Gaussian, Inc., Wallingford CT, 2009. Complete reference found on page S54. (n) Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. J. Chem. Phys. 2010, 132, 154104. (o) Lumo, version 1.0.1; Matthew T. Kieber-Emmons: Ephrata, PA, 2012. (p) Randall D.W., George S. D.-B., Hedman B., Hodgson K. O., Fujisawa K., Solomon E. I. J. Am. Chem. Soc. 2000, 122, 11620-11631. Examination of binding modes for Ph3CSNO at MesTpCuI We explored a range of potential binding modes of the S-nitrosothiol Ph3CSNO to the MesTpCuI fragment

(Tables S2 and S3; Fig. S28).q The lowest energy configuration is the 1-N-syn complex in which the

S-nitrosothiol is bound to the Cu center via the N atom with the RSNO in a syn conformation. The

B3LYP-D3/6-311G(d) optimized geometry closely matches the experimental structure (theory (exp):

Cu-N(O)SR 1.86 (1.893(4)), N-S 1.79 (1.755(4)), N-O 1.21 (1.206(5)), Cu…S 3.09 (3.044(4)) Å; Figs. 6A

and S25). While the 1-N-anti isomer is much higher in energy (G = +15.4 kcal/mol) due to steric

contact between the RSNO Ph3C and TpCu Mes groups, we identified three other energetically

competitive MesTpCu(RSNO) binding modes. For instance, the S-bound 1-S-syn and 1-S-anti

conformations are 7.5 and 8.7 kcal/mol higher in free energy. Anticipated in previous DFT studies

considering S-bound RSNOs to simple Lewis acids,r,s these 1-S binding modes feature activated S-NO

bond distances of 1.96 and 1.99 Å, respectively, compared to free Ph3CSNO (exp: S-NO = 1.792(5) Å

(anti)). The NO/SR binding mode is only 5.5 kcal/mol higher in free energy and conceptually

represents capture of NO at Cu (Cu-NO = 2.13 Å) with a significant interaction between the bound NO

and thiolate ligands (S…NO = 2.15 Å) leading to a lengthened Cu-SR bond (2.30 Å). Lastly, a binding

mode featuring a side-on 2-NO moiety is 12.8 kcal/mol higher in free energy, reminiscent of the binding

of C-nitroso compounds in low-coordinate -diketiminato complexes [Cu](2-ONPh).t.u




S27

Supplementary Table S2. Relative Energies for Alternative Binding Modes of the S-nitrosothiol

ONSCPh3 to the MesTpCuI fragment.

B3LYP-D3/6-311G(d)//B3LYP/6-311G(d)

ΔH ΔG

B3LYP-D3/6-311G(d)

ΔH ΔG MesTpCu-N(O)SCPh3-syn 0.0 0.0 0.0 0.0MesTpCu-N(O)SCPh3-anti 11.5 12.4 14.8 15.4MesTpCu- S(CPh3)NO-syn 6.2 5.9 9.0 7.5MesTpCu-S(CPh3)NO-anti 7.0 6.4 8.8 8.7MesTpCu-π-complex 13.0 12.7 12.3 12.8MesTpCu- S(CPh3)/NO 5.4 5.1 7.9 5.5

Table S3. Binding Energies of NO to Copper(II)-Thiolates.

B3LYP-D3/6-311G(d)//B3LYP/6-311G(d)

ΔH ΔG

B3LYP-D3/6-311G(d)

ΔH ΔGMesTpCu-SCPh3 + NO 0.0 0.0 0.0 0.0MesTpCu-N(O)SCPh3-syn -12.7 -1.3 -13.0 -2.1iPr2TpCu-SCPh3 + NO 0.0 0.0 0.0 0.0iPr2TpCu-N(O)SCPh3-syn -6.6 3.6 -6.2 3.4 References for S-nitrosothiol binding modes (q) Baciu, C.; Cho, K.-B.; Gauld, J. W. J. Phys. Chem. B 2005, 109, 1334-1336.

(r) Toubin, C.; Yeung, D. Y. H.; English, A. M.; Peslherbe, G. H. J. Am. Chem. Soc. 2002, 124,

14816-14817.

(s) Timerghazin, Q. K.; Peslherbe, G. H.; English, A. M. Org. Lett. 2007, 9, 3049-3052.

(t) Wiese, S.; Kapoor, P.; Williams, K. D.; Warren, T. H. J. Am. Chem. Soc. 2009, 131, 18105-18111.

(u) Williams, K. D.; Cardenas, A. J. P.; Oliva, J. D.; Warren, T. H. Eur. J. Inorg. Chem. 2013, 3812-3816.




S28

Supplementary Figure S28. Optimized structures (B3LYP-D3/6-311G(d)) of a range of binding modes for the S-nitrosothiol ONSCPh3 to the MesTpCuI fragment. Relative enthalpies H (and relative free energies G at 298 K given in parenthesis).

1-N-syn

0.0 (0.0)

1-N-anti

14.8 (15.4)

1-S-syn

9.0 (7.5)

1-S-anti

8.8 (8.7)

NO/SR 7.9 (5.5)

π

12.3 (12.8)




S29

Computed potential energy surface for NO capture/release

Supplementary Figure S29. Computed stationary points on the potential energy surface for NO

capture/release at the CuII/CuI center. Relative enthalpies, ΔH, (and relative free energies, ΔG, given in

parenthesis) are reported in kcal/mol with respect to the separated copper(II)-thiolate and nitric oxide. All

geometries and energies are at the B3LYP-D3/6-311G(d) level except for the transition state which was

optimized at the B3LYP/6-311G(d) level before applying a single point D3 energy correction.

Illustration of Cu-N(O)SR -backbonding in MesTpCu(1-N(O)SCPh3)

Supplementary Figure S30. Schematic depiction of Cu-N(O)SR -backbonding in TpCu(1-N(O)SR)

complexes along with contour plot of the LUMO (isovalue = 0.06) for MesTpCu(1-N(O)SCPh3)

illustrating the Cu-N * component of the Cu-N(O)SR -backbonding interaction. The Cu-N bonding

component of the Cu-N(O)SR backbonding interaction could not be readily identified due to significant

mixing of the -systems of the tris(pyrazolyl)borate ancillary ligand into the occupied frontier MOs.




S30

RS…NO interactions in the MesTpCu(NO)(SR) NO/SR isomer The close RS…NO separation of 2.15 Å observed in the DFT structure of the MesTpCu(NO)(SCPh3)

NO/SR isomer suggests that there is an interaction between the bound thiolate and NO ligands. This

may be conceptually viewed as a dative -interaction between a filled S-lone pair with the empty NO *

orbitals. While this -bonding interaction may be identified in frontier, filled MOs of MesTpCu(NO)(SCPh3) (HOMO and HOMO-4), the * component of this interaction is clearly seen in the

LUMO+1.

NNN

N

O

Cu

SR

-interactions between S-lone pair and NO * orbitals

LUMO+1 (-2.4842 eV)

Cu

S NO

NNN

N

O

Cu

SR

HOMO (-5.7699 eV)

HOMO-4 (-6.1847 eV)

Cu

S NO

NO

S

S NO

Cu

(filled) (empty)

Supplementary Figure S31. Schematic depiction of the -interaction present between a filled S-lone pair

and the NO * MOs. While filled levels with aspects of this -bonding interaction may be identified in

the frontier MOs of MesTpCu(NO)(SCPh3) (HOMO with isovalue = 0.065 and HOMO-4 with isovalue =

0.035), the * component of this interaction is clearly seen in the LUMO+1 (isovalue = 0.05).




S31

Cartesian coordinates of optimized structures NO B3LYP/6-311G(d) 2 opt-NO.out Energy: -81530.1749558 N 0.82323 2.01668 3.14283 O 1.70345 2.15348 3.86749 B3LYP-D3/6-311G(d) 2 optD3-NO.out Energy: -81530.1755211 N 0.82323 2.01668 3.14283 O 1.70345 2.15348 3.86749 Ph3CSNO-syn B3LYP/6-311G(d) 37 opt-ONSCPh3.out Energy: -791500.1008461 S -1.43524 -0.25850 0.31550 O 0.10048 1.13704 -1.32500 C -3.03958 0.41983 -0.50008 N 0.11847 0.33542 -0.45866 C -5.99044 -2.45484 0.91834 H -6.72419 -3.16741 1.28099 C -4.08070 -0.61234 -0.02535 C -4.89045 -1.32411 -0.91483 H -4.79254 -1.16760 -1.98099 C -5.83822 -2.23474 -0.44589 H -6.45725 -2.77195 -1.15741 C -3.34542 1.82175 0.04936 C -3.31295 1.48892 -2.80840 H -3.75974 2.35385 -2.33531 C -2.85934 0.42097 -2.02837 C -2.29310 -0.68155 -2.68521 H -1.94439 -1.53027 -2.10820 C -2.63124 4.08375 0.57907 H -1.83356 4.81697 0.64225 C -2.34341 2.79630 0.13858 H -1.33073 2.56072 -0.16211 C -2.62500 0.36637 -4.83573 H -2.52839 0.34815 -5.91647 C -3.93261 4.43116 0.93739 H -4.15645 5.43429 1.28577 C -4.25356 -0.83520 1.35102 H -3.65571 -0.27959 2.06526 C -5.19250 -1.74729 1.81713 H -5.30273 -1.90371 2.88540 C -4.65029 2.18704 0.39964 H -5.45240 1.46301 0.32831 C -3.19739 1.46123 -4.19819 H -3.55432 2.30584 -4.77892 C -4.94084 3.47822 0.83979 H -5.96132 3.73282 1.10811 C -2.17427 -0.70800 -4.07010 H -1.72519 -1.57079 -4.55176 B3LYP-D3/6-311G(d) 37 optD3- ONSCPh3-syn.out Energy: -791528.0631178 S 0.14137 -0.14004 2.21264 O 2.73974 0.06431 1.82949 C -0.10546 -0.01579 0.31724 N 1.92234 -0.11846 2.66149

C -4.15161 -1.53992 -0.18136 H -5.16511 -1.90794 -0.30376 C -1.52163 -0.59289 0.14061 C -1.79267 -1.67588 -0.69831 H -0.98951 -2.15543 -1.24187 C -3.09782 -2.14378 -0.85820 H -3.28440 -2.98470 -1.51849 C -0.05601 1.44997 -0.13658 C 1.68282 -0.38205 -1.47415 H 1.50124 0.62069 -1.83773 C 0.97593 -0.86518 -0.37077 C 1.24251 -2.17052 0.06755 H 0.69614 -2.57412 0.91207 C 0.98288 3.64478 -0.11521 H 1.72846 4.31750 0.29627 C 0.89627 2.34242 0.36688 H 1.59600 2.02036 1.12574 C 2.89592 -2.46402 -1.66712 H 3.64100 -3.07786 -2.16279 C 0.12065 4.08321 -1.11821 H 0.18582 5.10011 -1.49144 C -2.59642 0.01899 0.80608 H -2.41457 0.88401 1.43470 C -3.89438 -0.45107 0.65220 H -4.70746 0.03670 1.18005 C -0.90947 1.89817 -1.15145 H -1.64705 1.22552 -1.57166 C 2.63340 -1.17487 -2.11679 H 3.17259 -0.77392 -2.96911 C -0.82282 3.20164 -1.63724 H -1.49866 3.52462 -2.42266 C 2.19188 -2.95982 -0.57015 H 2.38353 -3.96459 -0.20736 Ph3CSNO-anti B3LYP/6-311G(d) 37 opt-ONSCPh3-anti.out Energy: -791500.0209956 S -1.43824 -0.27819 0.36918 O 0.98995 0.32928 -0.27858 C -3.01478 0.39292 -0.46485 N -0.10493 0.62161 -0.59484 C -6.04127 -2.44244 0.88045 H -6.79408 -3.14472 1.22361 C -4.08002 -0.62900 -0.01401 C -4.93713 -1.26131 -0.91832 H -4.85524 -1.05607 -1.97768 C -5.90975 -2.15823 -0.47411 H -6.56350 -2.63512 -1.19747 C -3.32984 1.80343 0.07185 C -3.23850 1.46545 -2.78075 H -3.67297 2.34095 -2.31621 C -2.81785 0.39038 -1.99268 C -2.27438 -0.72903 -2.64186 H -1.95163 -1.58290 -2.05836 C -2.63608 4.09251 0.50859 H -1.85210 4.84315 0.51093 C -2.34552 2.80084 0.08431 H -1.34370 2.57252 -0.25852 C -2.56018 0.31970 -4.79865 H -2.45425 0.29519 -5.87844 C -3.92349 4.42244 0.93027




S32

H -4.14949 5.42896 1.26740 C -4.23468 -0.91238 1.35277 H -3.60541 -0.41280 2.08111 C -5.19841 -1.81135 1.79456 H -5.29272 -2.01622 2.85615 C -4.62061 2.15135 0.48409 H -5.41164 1.41255 0.47299 C -3.10962 1.43065 -4.17009 H -3.44034 2.28198 -4.75655 C -4.91389 3.44726 0.91061 H -5.92350 3.68719 1.22891 C -2.14641 -0.76461 -4.02523 H -1.71847 -1.64172 -4.50029 B3LYP-D3/6-311G(d) 37 optD3-ONSCPh3-anti.out Energy: -791526.9699469 S -1.41610 -0.28080 0.38066 O 0.98850 0.33378 -0.36004 C -2.99716 0.38267 -0.44862 N -0.12015 0.60714 -0.64189 C -6.05237 -2.42411 0.87292 H -6.81604 -3.11724 1.21058 C -4.06541 -0.63553 -0.00655 C -4.91838 -1.26027 -0.91853 H -4.82462 -1.05538 -1.97685 C -5.90396 -2.14650 -0.48150 H -6.55543 -2.61909 -1.20964 C -3.31789 1.79042 0.08552 C -3.23605 1.46415 -2.75370 H -3.67189 2.33474 -2.28155 C -2.80370 0.38830 -1.97490 C -2.26193 -0.72772 -2.63027 H -1.93874 -1.58357 -2.05018 C -2.63956 4.08620 0.50184 H -1.86066 4.84201 0.50063 C -2.33856 2.79208 0.09365 H -1.33559 2.56617 -0.24624 C -2.56783 0.32785 -4.78031 H -2.47030 0.30742 -5.86094 C -3.93249 4.41253 0.91037 H -4.16691 5.42129 1.23472 C -4.23721 -0.90966 1.35973 H -3.61530 -0.40515 2.09112 C -5.21399 -1.79712 1.79466 H -5.32376 -1.99530 2.85596 C -4.61420 2.13359 0.48135 H -5.40045 1.38993 0.46637 C -3.11766 1.43448 -4.14400 H -3.45706 2.28586 -4.72532 C -4.91799 3.43186 0.89250 H -5.93163 3.67015 1.19875 C -2.14412 -0.75832 -4.01419 H -1.71806 -1.63262 -4.49585 MesTpCu-SCPh3 B3LYP/6-311G(d) 119 opt-MsTpCu-SCPh3.out Energy: -2837401.2171790 Cu -0.25490 -1.22467 -0.53222 S 0.52666 0.77995 -0.35317 N -0.05193 -3.03150 0.38446

N 1.49048 -1.94751 -2.03973 N -0.01161 -4.08894 -0.47319 N -1.64822 -1.90634 -1.82172 C 0.10456 -3.52581 1.62732 N 1.14434 -3.16945 -2.52867 C 0.06578 2.15108 0.87752 N -1.38820 -3.13116 -2.35314 C 5.21967 0.77225 -1.24831 H 6.07668 0.73347 -0.58006 C -4.92747 1.17211 -0.72194 H -5.56368 1.27145 0.15258 C 3.38733 -0.35677 -2.35133 C 4.49773 -0.39996 -1.48733 C -3.43113 -0.16461 -2.06309 C -3.66000 1.52253 3.04110 H -4.57168 1.37091 3.61086 C -1.28614 1.91331 1.56921 C 3.03321 0.85277 -2.97755 C 0.24826 -4.92270 1.55972 H 0.39664 -5.59950 2.38621 C 0.13231 -2.70029 2.86055 C -2.24002 2.93032 1.68449 H -2.06612 3.89003 1.21583 C -2.79474 -1.46889 -2.37356 C -3.41569 2.73694 2.41122 H -4.13538 3.54655 2.48523 C -3.28387 0.90925 -2.96260 C -4.26190 -0.03625 -0.93599 C 1.20144 2.20907 1.92660 C 0.79861 4.56161 0.33208 H 1.44214 4.55926 1.20236 C 0.16934 -5.23040 0.21505 H 0.23235 -6.17559 -0.30145 C 0.04552 3.42898 0.01449 C 3.78389 1.99894 -2.71440 H 3.50008 2.93208 -3.19450 C -0.77659 3.47964 -1.12159 H -1.37790 2.61732 -1.38506 C -0.94727 -2.75955 3.76310 C -3.97148 2.09695 -2.71110 H -3.86261 2.92434 -3.40815 C 1.27696 -1.94096 3.17591 C -4.79677 2.25014 -1.59572 C 3.55973 2.08436 2.50537 H 4.57965 1.86744 2.20349 C 2.64084 -1.61088 -2.64151 C 2.53231 1.94099 1.57670 H 2.76979 1.61843 0.57117 C -0.08061 5.74684 -1.58382 H -0.12713 6.63846 -2.20132 C 1.30872 -1.23534 4.37874 H 2.18605 -0.63873 4.61116 C 0.24800 -1.27222 5.28456 C 3.28551 2.50257 3.80601 H 4.08793 2.61705 4.52832 C -3.27576 -2.43524 -3.27380 H -4.17691 -2.37810 -3.86366 C -0.86648 -2.04479 4.96015 H -1.70099 -2.09000 5.65549 C -4.45281 -1.18497 0.02554 H -4.77717 -2.09259 -0.49151 H -5.19874 -0.94011 0.78330




S33

H -3.52271 -1.42840 0.54544 C -1.54153 0.69852 2.21839 H -0.80442 -0.09456 2.18201 C 1.84373 0.93761 -3.90091 H 0.91810 0.96976 -3.31937 H 1.78071 0.07626 -4.56979 H 1.88278 1.84348 -4.50984 C 2.05695 -3.59572 -3.42987 H 1.94449 -4.55055 -3.92079 C 4.92660 -1.68915 -0.82541 H 5.71589 -1.50823 -0.09260 H 5.30917 -2.40905 -1.55515 H 4.09410 -2.17639 -0.31320 C -2.71304 0.50353 2.94150 H -2.87583 -0.44537 3.43988 C 5.64830 3.24842 -1.55666 H 5.82878 3.82766 -2.46652 H 6.61719 3.03340 -1.09974 H 5.09642 3.89674 -0.86749 C -2.35443 -3.46491 -3.22720 H -2.31475 -4.40678 -3.75212 B -0.09736 -3.91664 -2.01212 H -0.15616 -5.00025 -2.52458 C 0.93924 2.62822 3.23675 H -0.07609 2.85087 3.53992 C 0.73653 5.71010 -0.46038 H 1.33422 6.57565 -0.19136 C -5.50152 3.55782 -1.33103 H -4.82672 4.27682 -0.85394 H -6.35910 3.42537 -0.66744 H -5.86059 4.01700 -2.25596 C 2.46507 -1.89871 2.24645 H 3.29799 -1.36173 2.70200 H 2.22338 -1.39467 1.30845 H 2.80533 -2.90654 1.99109 C 3.03510 -2.62841 -3.53717 H 3.91238 -2.64075 -4.16530 C -2.41242 0.78736 -4.19081 H -1.42163 0.39802 -3.94625 H -2.28275 1.75680 -4.67601 H -2.84606 0.10368 -4.92712 C 1.96895 2.77580 4.16530 H 1.73521 3.10767 5.17237 C 0.29816 -0.47424 6.56398 H 0.06406 0.57900 6.37603 H 1.29152 -0.50653 7.01919 H -0.42059 -0.84396 7.29891 C -2.18253 -3.57884 3.46472 H -2.57111 -3.38016 2.46264 H -2.97573 -3.36311 4.18372 H -1.97999 -4.65268 3.51261 C 4.87717 1.98377 -1.84823 C -0.84084 4.62262 -1.90910 H -1.48520 4.63403 -2.78277 B3LYP-D3/6-311G(d) 119 optD3-MsTpCu-SCPh3.out Energy: -2837534.3459368 Cu -1.38586 0.42530 -0.04274 S 0.53239 -0.06834 0.75135 N -2.54734 0.02933 1.92499 N -3.00735 -0.35575 -0.97138

N -3.83030 0.46897 1.88107 N -2.19520 2.26441 -0.03479 C -2.37673 -0.56461 3.11040 N -4.22783 0.08247 -0.56882 C 2.14645 -0.45127 -0.14339 N -3.52267 2.36128 0.24765 C -0.72652 -3.84355 -3.15233 H -0.54126 -4.91099 -3.06474 C 2.04008 3.71660 0.45758 H 2.77204 3.47306 1.22181 C -2.05876 -1.90834 -2.61243 C -1.82723 -3.29233 -2.49817 C -0.25397 3.75809 -0.28551 C 5.23984 1.67436 2.09161 H 6.00646 2.20109 2.65110 C 3.23897 0.31834 0.63526 C -1.20622 -1.10501 -3.39192 C -3.57452 -0.50164 3.85398 H -3.75252 -0.89572 4.84234 C -1.08020 -1.19468 3.45222 C 4.27729 0.98567 -0.01814 H 4.32046 0.99779 -1.09885 C -1.69246 3.50802 -0.04817 C 5.26820 1.65525 0.70214 H 6.05854 2.16972 0.16505 C 0.16227 4.25382 -1.53682 C 0.68554 3.49635 0.72711 C 2.27482 -1.97616 0.01990 C 2.97028 -0.79589 -2.51870 H 3.45777 -1.70400 -2.18506 C -4.46930 0.15960 3.03103 H -5.50551 0.42588 3.17490 C 2.17902 -0.06419 -1.62284 C -0.10405 -1.69593 -4.00924 H 0.57001 -1.07217 -4.58463 C 1.56568 1.10119 -2.08045 H 0.95226 1.67916 -1.40288 C -0.22547 -0.58627 4.38718 C 1.51615 4.49805 -1.74640 H 1.84272 4.87782 -2.71125 C -0.67909 -2.36121 2.77914 C 2.47225 4.22299 -0.76529 C 1.35829 -4.18009 -0.41524 H 0.57114 -4.79148 -0.84112 C -3.20332 -1.28077 -1.92243 C 1.27956 -2.79898 -0.52782 H 0.44101 -2.35193 -1.04687 C 2.55049 0.81371 -4.26917 H 2.69542 1.15681 -5.28883 C 0.57704 -2.90433 3.05388 H 0.90067 -3.78596 2.50958 C 1.44036 -2.31924 3.97785 C 2.43738 -4.77454 0.24171 H 2.49597 -5.85454 0.33339 C -2.72087 4.42827 0.21519 H -2.63287 5.50175 0.26785 C 1.01867 -1.16333 4.63885 H 1.68501 -0.69036 5.35699 C 0.27413 3.03204 2.10450 H -0.65541 2.46548 2.09336 H 0.13095 3.89278 2.76759 H 1.04073 2.39028 2.53975




S34

C 3.22915 0.33369 2.03968 H 2.43891 -0.17656 2.57349 C -1.47755 0.36943 -3.58200 H -1.21249 0.94385 -2.69206 H -2.53619 0.55935 -3.77463 H -0.89264 0.76948 -4.41041 C -5.18961 -0.56469 -1.25383 H -6.23050 -0.34869 -1.06928 C -2.73682 -4.17096 -1.67218 H -2.30061 -5.16159 -1.52720 H -3.71136 -4.30657 -2.15017 H -2.92650 -3.73768 -0.68804 C 4.21269 1.00375 2.75716 H 4.17245 1.00204 3.84215 C 1.40483 -3.66357 -4.48859 H 1.80732 -3.04617 -5.29422 H 1.21844 -4.66484 -4.88619 H 2.18477 -3.75534 -3.72479 C -3.85569 3.65674 0.40131 H -4.87064 3.93356 0.64124 B -4.37068 1.10635 0.58502 H -5.52205 1.41690 0.71811 C 3.35553 -2.57867 0.66449 H 4.14424 -1.96815 1.08438 C 3.15977 -0.35915 -3.82677 H 3.78248 -0.93952 -4.50033 C 3.93677 4.42398 -1.05924 H 4.31100 3.62159 -1.70371 H 4.53629 4.41548 -0.14806 H 4.11442 5.36954 -1.57934 C -1.55182 -2.97935 1.71538 H -1.19123 -3.96965 1.43333 H -1.55031 -2.35568 0.81778 H -2.59221 -3.06357 2.03983 C -4.58378 -1.44800 -2.13155 H -5.05982 -2.10638 -2.84035 C -0.83684 4.46356 -2.64973 H -1.36996 3.53438 -2.87418 H -0.34569 4.80145 -3.56465 H -1.59803 5.20142 -2.38408 C 3.43687 -3.96797 0.77449 H 4.28597 -4.41364 1.28293 C 2.82053 -2.87694 4.22155 H 3.57578 -2.28180 3.69657 H 2.91024 -3.90239 3.85862 H 3.07746 -2.86659 5.28462 C -0.62480 0.69565 5.07787 H -0.90037 1.46312 4.34999 H 0.19176 1.08666 5.68856 H -1.49314 0.55437 5.72740 C 0.16108 -3.05871 -3.89003 C 1.74577 1.53517 -3.39109 H 1.25795 2.44637 -3.71691 MesTpCu-N(O)SCPh3-syn B3LYP/6-311G(d) 121 opt-MsTpCu-NK1-ONSCPh3-syn.out Energy: -2918948.3368005 Cu 1.63471 -0.39387 0.40269 S -1.47400 -0.28886 0.38519 O 0.03058 1.08563 -1.26957

N 2.26003 -0.46674 2.38008 N 3.44166 0.80993 -0.13287 N 3.57619 -0.78391 2.51061 N 2.62416 -2.13419 -0.07472 C 1.77709 -0.27813 3.61915 N 4.55423 0.24481 0.41114 C -3.03847 0.42033 -0.48786 N 3.88157 -2.20064 0.43716 N 0.06617 0.29632 -0.36040 C 1.75679 4.85728 -1.84750 H 1.48403 5.83314 -1.45256 C -1.21163 -4.29493 -1.21182 H -2.08052 -4.52562 -0.60110 C 2.93827 2.76528 -1.59007 C 2.58328 4.02783 -1.08403 C 1.10374 -3.61693 -1.36740 C -6.01617 -2.45690 0.87086 H -6.75774 -3.17000 1.21645 C -4.09067 -0.60839 -0.02868 C 2.46670 2.35535 -2.85198 C 2.80324 -0.48021 4.56219 H 2.73016 -0.39299 5.63488 C 0.37146 0.11571 3.89290 C -4.89392 -1.30559 -0.93604 H -4.78294 -1.13532 -1.99876 C 2.39613 -3.29400 -0.71150 C -5.85094 -2.21717 -0.48916 H -6.46731 -2.73978 -1.21381 C 1.02494 -3.69692 -2.77042 C -0.02623 -3.91649 -0.58026 C -3.33202 1.82676 0.05598 C -3.39508 1.44178 -2.79641 H -3.90568 2.27206 -2.32535 C 3.92122 -0.79649 3.81315 H 4.93301 -1.02511 4.11079 C -2.84909 0.41970 -2.01313 C 1.64924 3.21543 -3.58306 H 1.28271 2.89265 -4.55428 C -2.19806 -0.63648 -2.66350 H -1.76868 -1.44714 -2.08674 C -0.51093 -0.79522 4.50188 C -0.18097 -4.08454 -3.36049 H -0.23513 -4.15387 -4.44428 C -0.06273 1.42223 3.59173 C -1.31023 -4.39041 -2.60111 C -2.60530 4.10367 0.49439 H -1.81098 4.84318 0.48907 C 3.85625 1.88438 -0.82137 C -2.33266 2.80926 0.06593 H -1.33775 2.57079 -0.28699 C -2.63477 0.36194 -4.82036 H -2.54605 0.34251 -5.90197 C -1.36492 1.79680 3.91992 H -1.69825 2.80300 3.68051 C -2.25233 0.91491 4.53960 C -3.88706 4.45155 0.91992 H -4.09919 5.46192 1.25487 C 3.53267 -4.11910 -0.61075 H 3.65509 -5.11378 -1.00991 C -1.80824 -0.37818 4.81235 H -2.48730 -1.08506 5.28288 C 0.03886 -3.86293 0.92753




S35

H 0.75150 -4.59592 1.31929 H -0.93756 -4.06757 1.36953 H 0.37080 -2.88483 1.28008 C -4.27541 -0.85054 1.34314 H -3.67928 -0.31320 2.07246 C 2.82581 0.99963 -3.40925 H 2.41993 0.20004 -2.78458 H 3.90911 0.85218 -3.44698 H 2.42973 0.87229 -4.41878 C 5.65341 0.95111 0.07207 H 6.63088 0.64658 0.41392 C 3.07665 4.49866 0.26475 H 2.59576 5.43678 0.55037 H 4.15782 4.66540 0.26759 H 2.87249 3.76185 1.04525 C -5.22161 -1.76799 1.78626 H -5.33964 -1.94125 2.85111 C 0.36251 5.36601 -3.89718 H 0.63865 5.38240 -4.95534 H 0.38503 6.39507 -3.53076 H -0.67535 5.01992 -3.84112 C 4.44412 -3.38469 0.12540 H 5.44590 -3.61941 0.45082 B 4.47494 -1.03527 1.27168 H 5.57703 -1.33760 1.63970 C -4.61691 2.19059 0.47358 H -5.41778 1.46218 0.46100 C -3.29075 1.41186 -4.18678 H -3.72273 2.21849 -4.77080 C -2.61075 -4.78197 -3.25964 H -3.27892 -3.91921 -3.35656 H -3.14373 -5.53813 -2.67757 H -2.44869 -5.18358 -4.26274 C 0.86191 2.41314 2.92652 H 0.36041 3.36816 2.76127 H 1.21426 2.04090 1.96232 H 1.75378 2.59754 3.53340 C 5.25674 2.01256 -0.71719 H 5.87808 2.77117 -1.16741 C 2.21514 -3.37397 -3.64407 H 2.67937 -2.42742 -3.35747 H 1.92061 -3.30240 -4.69317 H 2.99340 -4.13935 -3.57118 C -4.89168 3.49011 0.90266 H -5.89789 3.74488 1.22052 C -3.64332 1.36344 4.91903 H -4.10972 1.94638 4.12034 H -3.62298 1.99925 5.81098 H -4.29422 0.51450 5.14164 C -0.08714 -2.21193 4.81468 H 0.36640 -2.69557 3.94609 H -0.94249 -2.81402 5.12829 H 0.65545 -2.24908 5.61688 C 1.27828 4.47037 -3.09817 C -2.08893 -0.66322 -4.04965 H -1.56611 -1.48790 -4.52249 B3LYP-D3/6-311G(d) 121 optD3-MsTpCu-NK1-ONSCPh3-syn.out Energy: -2919078.3656136 Cu 1.74924 -0.03973 0.38677

S -1.31587 -0.02479 0.79081 O -0.14494 1.08876 -1.24605 N 2.62216 0.64105 2.08850 N 3.42992 0.68504 -0.75301 N 3.94966 0.41194 2.23683 N 2.73857 -1.83527 0.56981 C 2.20841 1.34481 3.14701 N 4.64066 0.42636 -0.19587 C -2.91519 0.12444 -0.23525 N 4.04426 -1.74414 0.93651 N 0.07100 0.46163 -0.23691 C 0.98376 3.32761 -3.63739 H 0.67706 4.36858 -3.70807 C -1.26421 -3.87746 0.73424 H -2.08639 -3.71577 1.42533 C 2.50233 1.65920 -2.78369 C 2.11923 3.00562 -2.89209 C 1.06421 -3.58846 0.15873 C -5.44482 -2.59273 2.03417 H -6.07423 -3.26547 2.60763 C -3.80994 -0.85632 0.54502 C 1.74566 0.65535 -3.41280 C 3.29673 1.57389 4.00991 H 3.28961 2.11280 4.94422 C 0.79144 1.76628 3.23608 C -4.45654 -1.92734 -0.07114 H -4.32911 -2.09544 -1.13214 C 2.43034 -3.13595 0.50862 C -5.27317 -2.78469 0.66747 H -5.77131 -3.60774 0.16582 C 0.83662 -4.23195 -1.07264 C 0.00716 -3.40270 1.06796 C -3.48337 1.54855 -0.18521 C -3.31538 0.27152 -2.74806 H -3.96274 1.12101 -2.57198 C 4.37781 0.96577 3.38940 H 5.41379 0.89133 3.68251 C -2.65487 -0.33857 -1.67806 C 0.62967 1.01952 -4.16469 H 0.03164 0.24276 -4.63038 C -1.81861 -1.42924 -1.94890 H -1.29252 -1.92328 -1.14370 C -0.08644 1.11199 4.11359 C -0.44300 -4.70440 -1.35956 H -0.62057 -5.20741 -2.30712 C 0.32416 2.80071 2.40055 C -1.50535 -4.54112 -0.46838 C -3.20677 3.94433 -0.45400 H -2.55204 4.79014 -0.63874 C 3.65074 1.28167 -1.92780 C -2.67010 2.66147 -0.42661 H -1.61406 2.52432 -0.60943 C -2.32390 -1.28771 -4.30629 H -2.19269 -1.65084 -5.32072 C -1.01263 3.18038 2.48571 H -1.38016 3.97418 1.84347 C -1.90564 2.54570 3.35189 C -4.57065 4.14544 -0.24638 H -4.98651 5.14765 -0.26316 C 3.56277 -3.90546 0.83742 H 3.63151 -4.98096 0.88147 C -1.42526 1.51112 4.15240




S36

H -2.10852 0.99637 4.82351 C 0.24193 -2.72303 2.39489 H 0.92273 -3.30884 3.02071 H -0.69247 -2.57965 2.93888 H 0.70467 -1.74492 2.26266 C -4.00593 -0.65784 1.92240 H -3.53634 0.18600 2.41643 C 2.07131 -0.80338 -3.20606 H 1.84118 -1.10161 -2.17922 H 3.13328 -1.01343 -3.35796 H 1.49020 -1.43937 -3.87584 C 5.62429 0.86013 -1.01348 H 6.66132 0.73549 -0.74104 C 2.89193 4.08533 -2.17208 H 2.41766 5.06145 -2.29506 H 3.92013 4.16255 -2.53584 H 2.95631 3.87203 -1.10139 C -4.80550 -1.52162 2.66024 H -4.93615 -1.35351 3.72445 C -1.04037 2.70671 -5.01752 H -1.20754 2.04808 -5.87363 H -1.02053 3.73697 -5.38203 H -1.90906 2.60330 -4.35874 C 4.55797 -2.97952 1.10196 H 5.58806 -3.10921 1.39628 B 4.72422 -0.35949 1.13354 H 5.86925 -0.50846 1.46071 C -4.85296 1.75986 0.01067 H -5.50975 0.91686 0.18534 C -3.15249 -0.20011 -4.05024 H -3.67276 0.29355 -4.86462 C -2.88276 -5.03217 -0.83446 H -3.34079 -4.37515 -1.58141 H -3.54574 -5.05541 0.03140 H -2.84681 -6.03694 -1.26475 C 1.24397 3.46013 1.40050 H 0.75404 4.29839 0.90162 H 1.55885 2.74965 0.63268 H 2.15841 3.82735 1.87428 C 5.03843 1.42022 -2.13645 H 5.53206 1.85746 -2.99026 C 1.95527 -4.40981 -2.07152 H 2.50724 -3.47936 -2.21880 H 1.57059 -4.73520 -3.04052 H 2.68135 -5.15491 -1.73397 C -5.39217 3.04582 -0.01844 H -6.45690 3.18229 0.14155 C -3.35366 2.96576 3.38816 H -3.80243 2.91757 2.39300 H -3.45807 3.99818 3.73656 H -3.94285 2.33225 4.05575 C 0.39994 -0.01908 4.98758 H 0.97398 -0.74666 4.41027 H -0.43457 -0.54221 5.45916 H 1.06053 0.34275 5.78113 C 0.22546 2.34859 -4.27890 C -1.65564 -1.89860 -3.24626 H -0.99628 -2.74184 -3.41955 MesTpCu-N(O)SCPh3-anti B3LYP/6-311G(d)

121 opt-MsTpCu-NK1-ONSCPh3-anti.out Energy: -2918933.5564723 Cu -1.27441 0.57832 0.49158 S 1.46089 -1.64353 0.69081 O -1.05358 -2.04600 0.76542 N -1.91785 2.43130 -0.12947 N -1.71129 0.93708 2.48583 N -3.13345 2.73362 0.41394 N -3.47394 -0.27952 0.10987 C -1.61791 3.43521 -0.98201 N -2.92182 1.54102 2.64111 C 2.71757 -1.01711 -0.58956 N -4.33655 0.53484 0.77434 N -0.39002 -1.11727 0.41960 C 2.51192 0.35815 4.33325 H 3.40825 0.97286 4.34814 C -2.98111 -3.33242 -3.29630 H -2.85166 -3.20093 -4.36791 C 0.13069 0.16244 3.98594 C 1.28994 0.95588 4.01214 C -3.64486 -2.42436 -1.15551 C 5.85725 -3.88118 0.38873 H 6.63732 -4.59195 0.64204 C 3.83773 -2.03385 -0.27347 C 0.20434 -1.21081 4.29530 C -2.66760 4.37262 -0.99248 H -2.72702 5.27294 -1.58237 C -0.37093 3.56415 -1.77723 C 4.22412 -3.02865 -1.17736 H 3.74709 -3.09572 -2.14618 C -4.20458 -1.31126 -0.34246 C 5.22788 -3.93953 -0.85030 H 5.51435 -4.69763 -1.57231 C -3.36878 -3.66928 -0.55497 C -3.46633 -2.26070 -2.54058 C 2.20599 -1.16995 -2.03579 C 4.50141 0.80301 -0.41496 H 5.24933 0.06630 -0.68193 C -3.59708 3.88867 -0.09673 H -4.55235 4.28027 0.21615 C 3.15843 0.42285 -0.29505 C 1.44265 -1.76439 4.61541 H 1.49900 -2.82492 4.84775 C 2.22561 1.40665 0.03965 H 1.17338 1.14948 0.11910 C -0.01628 2.60007 -2.74198 C -2.88042 -4.71054 -1.34495 H -2.65817 -5.66549 -0.87448 C 0.41087 4.73229 -1.64166 C -2.67553 -4.56347 -2.71810 C 0.85603 -2.28690 -3.72291 H 0.07002 -2.99609 -3.95882 C -1.19005 0.78643 3.71616 C 1.21123 -2.08917 -2.39002 H 0.71160 -2.66910 -1.62584 C 3.95896 3.08271 0.16630 H 4.26468 4.10733 0.35214 C 1.50601 4.91999 -2.48662 H 2.10565 5.82001 -2.37262 C 1.85668 3.98921 -3.46205 C 1.49623 -1.57879 -4.73606




S37

H 1.22363 -1.73660 -5.77477 C -5.55335 -1.15762 0.04083 H -6.37568 -1.81967 -0.18254 C 1.08437 2.83345 -3.56629 H 1.34155 2.08718 -4.31147 C -3.84217 -0.96939 -3.22775 H -3.43733 -0.10096 -2.70827 H -4.92955 -0.84145 -3.25363 H -3.48121 -0.95189 -4.25828 C 4.47928 -1.98671 0.97631 H 4.19887 -1.22488 1.69418 C -1.03244 -2.07782 4.29390 H -1.53909 -2.05574 3.32637 H -1.76029 -1.74104 5.03798 H -0.78144 -3.11687 4.51516 C -3.16065 1.76713 3.94720 H -4.07913 2.23754 4.26258 C 1.22666 2.44041 3.74141 H 0.79040 2.97737 4.59059 H 0.60675 2.67014 2.87313 H 2.22271 2.84945 3.56382 C 5.47607 -2.89942 1.30236 H 5.95913 -2.83964 2.27241 C 3.93120 -1.62554 5.01111 H 3.94625 -1.93170 6.06246 H 4.76199 -0.93235 4.86055 H 4.12772 -2.52142 4.41474 C -5.58837 0.02793 0.74656 H -6.40531 0.54662 1.22473 B -3.86306 1.83597 1.44639 H -4.82003 2.43300 1.85858 C 2.83145 -0.45335 -3.06473 H 3.59791 0.27345 -2.82752 C 4.89867 2.11945 -0.18588 H 5.94726 2.38512 -0.27818 C -2.13769 -5.70780 -3.54389 H -1.09494 -5.92860 -3.29146 H -2.17772 -5.48575 -4.61280 H -2.70702 -6.62664 -3.37496 C 0.12005 5.78998 -0.59814 H -0.62624 6.51330 -0.94123 H 1.02651 6.35337 -0.36452 H -0.26320 5.36153 0.32960 C -2.08110 1.30261 4.67424 H -1.94158 1.32794 5.74362 C -3.62365 -3.90402 0.91456 H -3.29151 -3.06141 1.52089 H -3.10633 -4.80054 1.26292 H -4.69201 -4.03959 1.11345 C 2.48732 -0.66072 -4.39843 H 2.99733 -0.09777 -5.17412 C 3.05945 4.20719 -4.34694 H 3.19815 5.26489 -4.58561 H 2.96972 3.66114 -5.28916 H 3.97697 3.86346 -3.85654 C -0.82142 1.33788 -2.91703 H -0.37359 0.67963 -3.66115 H -1.84748 1.56021 -3.22416 H -0.89063 0.78118 -1.98115 C 2.60912 -0.99717 4.64179 C 2.61828 2.71991 0.27165 H 1.87217 3.46059 0.53059

B3LYP-D3/6-311G(d) 121 optD3-MsTpCu-NK1-ONSCPh3-anti.out Energy: -2919063.6852288 Cu -1.46007 -0.19920 0.46467 S 1.52548 -1.37631 -0.91516 O -0.88010 -1.68503 -1.65057 N -2.16779 1.28370 1.76411 N -1.96245 -1.68917 1.77542 N -3.40115 0.98561 2.26197 N -3.46421 -0.21675 -0.46578 C -1.85873 2.51787 2.20639 N -3.17152 -1.52298 2.37491 C 2.71409 0.04390 -0.56334 N -4.43511 -0.43834 0.45868 N -0.33744 -0.93158 -0.89387 C 2.19326 -3.79350 1.82595 H 3.13924 -3.66775 2.34700 C -2.15441 1.62790 -4.30555 H -1.96120 2.66445 -4.57151 C -0.17860 -3.38652 1.70477 C 1.03963 -3.23097 2.37984 C -3.25982 0.01418 -2.88941 C 6.24700 -2.26667 -1.64634 H 7.12258 -2.84899 -1.91477 C 3.99149 -0.73999 -0.94414 C -0.23996 -4.12027 0.50276 C -2.91729 3.01700 2.98992 H -2.96885 3.97935 3.47267 C -0.57391 3.17834 1.89585 C 4.53123 -0.67035 -2.23462 H 4.07283 -0.02704 -2.97465 C -4.05130 -0.27583 -1.66899 C 5.65134 -1.42169 -2.57980 H 6.05646 -1.34609 -3.58376 C -2.72613 -1.02786 -3.66709 C -3.01116 1.35370 -3.23705 C 2.50740 1.25918 -1.49040 C 3.90115 0.93772 1.51288 H 4.82264 0.96910 0.94446 C -3.86736 2.01460 2.99559 H -4.83652 1.95533 3.46608 C 2.72182 0.47450 0.91206 C 0.93158 -4.66883 -0.01090 H 0.88895 -5.22487 -0.94375 C 1.57276 0.42034 1.69640 H 0.63862 0.07521 1.27242 C -0.17106 3.35662 0.55857 C -1.86953 -0.71188 -4.72279 H -1.42927 -1.51954 -5.30191 C 0.25572 3.63247 2.94096 C -1.55056 0.60839 -5.04236 C 1.32521 2.51323 -3.20124 H 0.45420 2.60418 -3.83976 C -1.43913 -2.83023 2.24698 C 1.41335 1.41742 -2.34099 H 0.61591 0.68995 -2.36464 C 2.77144 1.22282 3.62761 H 2.78756 1.50446 4.67540 C 1.49064 4.19720 2.62656 H 2.14445 4.51133 3.43607 C 1.93044 4.32827 1.31161




S38

C 2.33476 3.46734 -3.23789 H 2.26850 4.31372 -3.91382 C -5.42346 -0.55267 -1.52006 H -6.15876 -0.65262 -2.30309 C 1.07269 3.92429 0.29075 H 1.37875 4.04624 -0.74123 C -3.72441 2.48170 -2.53169 H -3.80555 2.30909 -1.45961 H -4.74574 2.57842 -2.91545 H -3.21928 3.43640 -2.68881 C 4.57998 -1.61960 -0.02337 H 4.15044 -1.72352 0.96466 C -1.55876 -4.33313 -0.19936 H -2.08615 -3.39215 -0.35818 H -2.22070 -4.96817 0.39812 H -1.41722 -4.80671 -1.17202 C -3.40238 -2.53908 3.22865 H -4.31951 -2.57926 3.79592 C 1.11505 -2.51407 3.70537 H 0.96777 -3.21658 4.53329 H 0.34703 -1.74650 3.79624 H 2.08514 -2.03336 3.84321 C 5.70113 -2.36691 -0.36820 H 6.14229 -3.03651 0.36277 C 3.41619 -5.07824 0.01995 H 3.24550 -6.07790 -0.38908 H 4.22793 -5.14701 0.74792 H 3.76729 -4.44307 -0.79900 C -5.62094 -0.64410 -0.15230 H -6.51308 -0.83066 0.42593 B -4.10917 -0.35906 1.96904 H -5.12467 -0.42701 2.60555 C 3.50885 2.24191 -1.52228 H 4.37232 2.14866 -0.87681 C 3.92625 1.30777 2.85455 H 4.85623 1.65214 3.29603 C -0.56069 0.91932 -6.13800 H 0.46691 0.86220 -5.76206 H -0.70486 1.92528 -6.54044 H -0.64148 0.21184 -6.96717 C -0.12532 3.48947 4.39666 H -0.77701 4.30503 4.72630 H 0.76369 3.50974 5.03110 H -0.66439 2.56134 4.59429 C -2.31829 -3.39967 3.18497 H -2.17773 -4.31804 3.73274 C -3.08175 -2.46731 -3.38991 H -3.18877 -2.65767 -2.32321 H -2.31855 -3.14456 -3.77815 H -4.03401 -2.72774 -3.86459 C 3.43168 3.32583 -2.38734 H 4.22822 4.06283 -2.39341 C 3.31381 4.84303 1.00892 H 3.63358 5.59830 1.73175 H 3.37478 5.27804 0.00930 H 4.03740 4.02108 1.05199 C -1.06351 2.96421 -0.58832 H -0.81507 3.52091 -1.49199 H -2.11176 3.12977 -0.34907 H -0.96284 1.90568 -0.83446 C 2.16110 -4.51206 0.63330 C 1.59212 0.78543 3.03633

H 0.67593 0.72607 3.61078 MesTpCu- S(CPh3)NO-syn B3LYP/6-311G(d) 121 opt-MsTpCu-SK1-ONSCPh3-syn.out Energy: -2918934.4356438 Cu -0.00685 -1.18138 0.76183 S 0.46799 0.89606 0.06261 O 2.98369 1.70465 -0.52958 N -0.14780 -0.98591 2.90884 N 1.71727 -2.55450 0.96182 N -0.10737 -2.21562 3.48876 N -1.39544 -2.72880 0.69013 C -0.33330 -0.10077 3.89872 N 1.40287 -3.49623 1.89562 C -0.17755 2.07279 -1.33664 N -1.11811 -3.65194 1.65305 N 2.40292 1.03978 0.22319 C 5.45576 -0.43078 -0.95857 H 6.17732 0.30741 -0.61795 C -5.11937 -1.61116 -2.16895 H -6.17610 -1.36164 -2.10919 C 3.73372 -2.04892 -0.44754 C 4.68343 -1.10468 -0.01108 C -3.12438 -2.48801 -1.11452 C 3.60690 -2.33304 -1.82061 C -0.40939 -0.77208 5.13642 H -0.55386 -0.33054 6.11034 C -0.46439 1.36584 3.69077 C -2.47639 -3.18217 0.02524 C -2.40843 -2.23929 -2.30422 C -4.49550 -2.16287 -1.04676 C -0.26224 -2.10961 4.82489 H -0.25732 -2.98861 5.45109 C 4.39826 -1.63410 -2.73478 H 4.30329 -1.86277 -3.79366 C -1.73662 1.92561 3.46799 C -3.07161 -1.68223 -3.39686 H -2.50886 -1.49228 -4.30638 C 0.66044 2.20100 3.81075 C -4.42954 -1.36397 -3.35376 C 2.96836 -2.83585 0.55541 C 0.48928 3.58529 3.72600 H 1.35935 4.22826 3.83654 C -0.76296 4.16186 3.51221 C -2.88298 -4.41803 0.56529 H -3.70178 -5.03631 0.23376 C -1.86173 3.31246 3.37675 H -2.84547 3.74039 3.20244 C -5.31669 -2.38556 0.20457 H -5.66268 -3.42039 0.28825 H -6.20642 -1.75123 0.19926 H -4.74967 -2.17035 1.11193 C 2.66917 -3.41294 -2.30318 H 1.65357 -3.25676 -1.93969 H 2.98324 -4.39713 -1.94179 H 2.63867 -3.45202 -3.39410 C 2.42823 -4.35437 2.06830 H 2.35092 -5.16793 2.77298 C 4.88781 -0.82727 1.45947 H 5.49993 0.06485 1.60802




S39

H 5.39096 -1.66273 1.95623 H 3.93783 -0.67903 1.97557 C 6.14042 0.10068 -3.33261 H 6.25747 -0.45343 -4.26715 H 7.13887 0.32812 -2.95058 H 5.66356 1.05608 -3.57793 C -1.99581 -4.67211 1.59019 H -1.92193 -5.50118 2.27659 B 0.05737 -3.50356 2.65264 H 0.04051 -4.44815 3.39453 C -5.11797 -0.73790 -4.54177 H -4.95838 0.34586 -4.56407 H -6.19715 -0.90679 -4.51718 H -4.73755 -1.13946 -5.48461 C 2.04158 1.62379 4.00680 H 2.76988 2.40799 4.22443 H 2.37325 1.10112 3.10433 H 2.07000 0.89598 4.82102 C 3.45548 -3.97201 1.23017 H 4.42234 -4.43575 1.11042 C -0.94866 -2.59887 -2.42107 H -0.35282 -2.09334 -1.65892 H -0.55164 -2.32227 -3.39766 H -0.79467 -3.67266 -2.27497 C -0.92327 5.65923 3.40189 H -0.12155 6.18875 3.92265 H -1.87388 5.99393 3.82499 H -0.90405 5.98508 2.35582 C -2.95904 1.04743 3.34749 H -2.84129 0.30758 2.55239 H -3.84755 1.64111 3.12532 H -3.14372 0.49110 4.27146 C 5.32269 -0.67139 -2.32596 C 0.67980 3.34870 -1.25036 C 2.17869 5.72558 -1.06367 C 0.85401 3.99588 -0.01731 C 1.26224 3.92071 -2.38486 C 2.00278 5.09940 -2.29219 C 1.59876 5.16597 0.07464 H 0.40845 3.57969 0.87854 H 1.14663 3.44844 -3.35159 H 2.44632 5.52122 -3.18864 H 1.72679 5.64009 1.04252 H 2.76146 6.63828 -0.99040 C -1.64255 2.33790 -0.95211 C -4.36358 2.76913 -0.37457 C -2.15797 3.63473 -0.84906 C -2.52087 1.26005 -0.77577 C -3.86274 1.47274 -0.48061 C -3.50668 3.84766 -0.56581 H -1.51221 4.48946 -0.99911 H -2.15705 0.24380 -0.87144 H -4.51513 0.61830 -0.34916 H -3.88243 4.86384 -0.49721 H -5.41287 2.93422 -0.15075 C -0.07249 1.40354 -2.71206 C 0.21032 0.40427 -5.33231 C 1.00978 0.58772 -3.05848 C -1.01750 1.69907 -3.70320 C -0.87699 1.20738 -4.99938 C 1.15175 0.09611 -4.35313 H 1.76093 0.32906 -2.32425

H -1.86765 2.32649 -3.46567 H -1.62230 1.45648 -5.74825 H 2.00500 -0.53070 -4.58955 H 0.32248 0.02169 -6.34187 B3LYP-D3/6-311G(d) 121 optD3-MsTpCu-SK1-ONSCPh3-syn.out Energy: -2919069.5694622 Cu 0.51397 -1.32944 0.17549 S 0.13651 0.79573 0.54261 O 2.06951 2.63096 0.10722 N 0.82540 -2.16538 2.09575 N 2.58057 -1.95210 -0.32960 N 1.42116 -3.38200 2.10017 N -0.25516 -3.11003 -0.50863 C 0.59862 -1.82787 3.36747 N 2.78040 -3.26419 -0.01990 C -1.03704 2.06681 -0.29432 N 0.43346 -4.20198 -0.07705 N 1.91754 1.59975 0.61429 C 4.86734 2.07175 -0.66213 H 5.32934 2.73882 0.06085 C -4.54400 -1.89705 -2.19399 H -5.59754 -1.94456 -1.92987 C 3.97015 -0.09633 -1.22187 C 4.59372 0.75643 -0.29180 C -2.27639 -2.66155 -1.86066 C 3.65623 0.36595 -2.51005 C 1.07607 -2.84353 4.22101 H 1.02893 -2.86889 5.29854 C -0.16894 -0.60326 3.68708 C -1.30859 -3.56532 -1.20639 C -1.83618 -1.74818 -2.83779 C -3.64549 -2.73847 -1.53771 C 1.58561 -3.81033 3.36978 H 2.04162 -4.76727 3.57291 C 3.91637 1.69932 -2.83024 H 3.65941 2.06637 -3.82059 C -1.54809 -0.58669 3.40700 C -2.76805 -0.92127 -3.46208 H -2.41981 -0.21061 -4.20276 C 0.45924 0.53007 4.22284 C -4.12465 -0.97212 -3.14887 C 3.73575 -1.50960 -0.84671 C -0.31779 1.64943 4.53015 H 0.16582 2.52575 4.95556 C -1.69027 1.68168 4.28045 C -1.29323 -4.97306 -1.22674 H -1.99419 -5.62561 -1.72197 C -2.28446 0.55864 3.70275 H -3.34372 0.58027 3.46717 C -4.14915 -3.67742 -0.46516 H -4.15554 -4.71815 -0.79992 H -5.17092 -3.42465 -0.17209 H -3.51829 -3.64009 0.42653 C 3.07532 -0.58051 -3.52992 H 2.14776 -1.02551 -3.17242 H 3.76168 -1.40897 -3.72679 H 2.87358 -0.07885 -4.47821 C 4.03177 -3.64250 -0.35022 H 4.36574 -4.65232 -0.16783




S40

C 4.92342 0.26116 1.09476 H 5.31581 1.06525 1.72059 H 5.66306 -0.54380 1.06917 H 4.03297 -0.14624 1.57977 C 4.71807 4.02571 -2.25100 H 4.78923 4.18850 -3.32920 H 5.62611 4.42192 -1.78922 H 3.87802 4.62492 -1.88263 C -0.17223 -5.32853 -0.50113 H 0.24126 -6.29544 -0.26012 B 1.73246 -4.08589 0.76002 H 2.16319 -5.18679 0.97214 C -5.09963 -0.00948 -3.77776 H -5.18934 0.89697 -3.16841 H -6.09945 -0.44201 -3.86560 H -4.77601 0.29945 -4.77462 C 1.95937 0.57444 4.38011 H 2.27851 1.46189 4.93087 H 2.43421 0.60410 3.39323 H 2.35115 -0.30726 4.89127 C 4.68347 -2.55039 -0.89001 H 5.69719 -2.49250 -1.25458 C -0.38085 -1.64090 -3.21118 H 0.17974 -1.13154 -2.42507 H -0.25017 -1.06675 -4.12850 H 0.08161 -2.62266 -3.33509 C -2.50334 2.92179 4.55642 H -2.02210 3.56535 5.29697 H -3.50265 2.67385 4.92297 H -2.63345 3.51023 3.64181 C -2.21350 -1.77877 2.76240 H -1.87051 -1.90044 1.73147 H -3.29790 -1.66488 2.74651 H -1.96569 -2.70719 3.28346 C 4.51154 2.57017 -1.91550 C -0.59806 3.45391 0.20845 C 0.15830 5.97729 1.19663 C -0.42058 3.66610 1.58243 C -0.39859 4.52911 -0.65963 C -0.02442 5.78022 -0.16814 C -0.04414 4.90996 2.07172 H -0.57049 2.84518 2.27007 H -0.52228 4.39915 -1.72649 H 0.12876 6.60029 -0.86257 H 0.09166 5.04234 3.14052 H 0.45542 6.94978 1.57595 C -2.42773 1.68472 0.23483 C -4.99296 0.96218 1.12523 C -3.27302 2.62913 0.82634 C -2.89930 0.37724 0.06835 C -4.16198 0.01830 0.52572 C -4.54712 2.27276 1.26336 H -2.94398 3.65268 0.94373 H -2.27462 -0.36558 -0.41454 H -4.49474 -1.00342 0.40748 H -5.18460 3.02377 1.71906 H -5.97910 0.67711 1.47798 C -0.97940 1.98816 -1.81909 C -0.84996 2.21576 -4.61852 C 0.21058 1.72653 -2.50192 C -2.11016 2.34584 -2.56355 C -2.04495 2.46783 -3.94851

C 0.27397 1.83830 -3.88792 H 1.10487 1.44675 -1.96176 H -3.04459 2.54675 -2.05412 H -2.93390 2.75132 -4.50287 H 1.21026 1.63112 -4.39272 H -0.79652 2.30663 -5.69870 MesTpCu- S(CPh3)NO-anti B3LYP/6-311G(d) 121 opt-MsTpCu-SK1-ONSCPh3-anti.out Energy: -2918934.2455776 Cu 0.39263 -1.11273 0.75684 S -0.04380 0.96470 0.08524 O 2.37720 1.73440 0.84014 N 0.77335 -0.96399 2.83666 N 2.50387 -1.97183 0.43804 N 1.28494 -2.12577 3.32172 N -0.43419 -2.99517 0.86006 C 0.62774 -0.13695 3.88376 N 2.66196 -2.96469 1.36008 C -1.07636 1.91358 -1.25314 N 0.28636 -3.80081 1.68883 N 1.60856 2.02532 0.02292 C 5.01634 1.12304 -2.05957 H 5.55270 2.03877 -1.82363 C -4.82245 -2.87069 -1.09291 H -5.86744 -2.86790 -0.79174 C 3.96955 -0.92591 -1.31378 C 4.68246 0.25099 -1.01857 C -2.49653 -3.23942 -0.53921 C 3.66357 -1.24271 -2.65255 C 1.06037 -0.77851 5.06176 H 1.05760 -0.37709 6.06313 C 0.04187 1.22344 3.77542 C -1.46610 -3.73165 0.40732 C -2.14045 -2.87480 -1.85353 C -3.85330 -3.23177 -0.15424 C 1.46541 -2.03518 4.65565 H 1.86394 -2.86777 5.21472 C 4.03527 -0.35463 -3.66240 H 3.81642 -0.61275 -4.69597 C -1.34100 1.37206 3.53899 C -3.14245 -2.51283 -2.75449 H -2.85846 -2.22668 -3.76302 C 0.84432 2.35902 3.98402 C -4.49059 -2.50750 -2.39727 C 3.67039 -1.89769 -0.22810 C 0.25019 3.62517 3.95270 H 0.87469 4.50032 4.11449 C -1.11423 3.79410 3.72804 C -1.39651 -5.02962 0.94890 H -2.06937 -5.85115 0.76105 C -1.89139 2.65224 3.51593 H -2.95704 2.76172 3.33144 C -4.29012 -3.59910 1.24673 H -4.30461 -4.68235 1.40013 H -5.29990 -3.23213 1.44455 H -3.62238 -3.18426 2.00444 C 2.98695 -2.54622 -3.00175 H 2.03915 -2.66058 -2.47472 H 3.60736 -3.40184 -2.71846




S41

H 2.79066 -2.61522 -4.07382 C 3.89402 -3.50668 1.26972 H 4.19141 -4.30894 1.92726 C 5.15424 0.55760 0.38368 H 5.33146 1.62710 0.51359 H 6.09582 0.03885 0.59522 H 4.43906 0.23690 1.14010 C 5.04370 1.80886 -4.49435 H 5.36182 1.28508 -5.39989 H 5.84770 2.48750 -4.20050 H 4.17982 2.42598 -4.76514 C -0.27338 -5.02470 1.75078 H 0.16970 -5.79964 2.35670 B 1.58074 -3.33105 2.39952 H 1.98908 -4.23737 3.07375 C -5.55415 -2.08221 -3.37957 H -5.73317 -1.00272 -3.32150 H -6.50726 -2.57944 -3.18262 H -5.26474 -2.30803 -4.40879 C 2.32653 2.24157 4.25532 H 2.82622 3.20170 4.10858 H 2.80180 1.50845 3.60183 H 2.52348 1.92338 5.28405 C 4.57777 -2.85633 0.26398 H 5.58592 -3.03425 -0.07692 C -0.70213 -2.90568 -2.30718 H -0.07396 -2.26107 -1.69019 H -0.60891 -2.57473 -3.34183 H -0.28566 -3.91508 -2.22849 C -1.74744 5.16502 3.72486 H -0.99774 5.95468 3.81334 H -2.44604 5.28163 4.55990 H -2.31623 5.34392 2.80722 C -2.22948 0.16735 3.34503 H -1.90248 -0.44160 2.50050 H -3.26246 0.46799 3.16442 H -2.20995 -0.48291 4.22551 C 4.69739 0.84400 -3.38651 C -0.53581 3.35364 -1.26952 C 0.38613 6.01598 -1.25318 C -0.49638 4.09852 -0.07897 C -0.10949 3.97198 -2.44679 C 0.34480 5.29233 -2.43849 C -0.03934 5.41021 -0.07046 H -0.82126 3.64379 0.84935 H -0.13040 3.43192 -3.38395 H 0.66847 5.74900 -3.36853 H -0.01182 5.95828 0.86577 H 0.74461 7.04044 -1.24692 C -2.52555 1.85927 -0.73742 C -5.20863 1.70907 0.10815 C -3.33967 2.99777 -0.71849 C -3.09019 0.63845 -0.34708 C -4.41241 0.56561 0.07878 C -4.66828 2.92357 -0.30134 H -2.94354 3.95290 -1.03701 H -2.50098 -0.27029 -0.38342 H -4.81748 -0.39388 0.37716 H -5.27702 3.82245 -0.29885 H -6.24065 1.65038 0.43955 C -0.94569 1.23543 -2.62223 C -0.68257 0.22097 -5.23702

C 0.28463 0.75558 -3.08623 C -2.04322 1.18749 -3.49084 C -1.91324 0.68720 -4.78512 C 0.41487 0.25752 -4.37940 H 1.15565 0.77439 -2.44250 H -3.00822 1.55161 -3.16184 H -2.77970 0.66658 -5.43880 H 1.38212 -0.10288 -4.70972 H -0.57843 -0.16781 -6.24516 B3LYP-D3/6-311G(d) 121 optD3-MsTpCu-SK1-ONSCPh3-anti.out Energy: -2919069.8707293 Cu 1.43043 -0.23831 0.15492 S -0.61199 0.41119 0.55108 O 0.14031 2.53659 1.95347 N 2.30252 -0.42483 2.08879 N 3.06294 1.04233 -0.44974 N 3.65122 -0.56660 2.07677 N 2.48611 -1.90155 -0.47616 C 1.91228 -0.43660 3.36865 N 4.27709 0.51996 -0.12826 C -2.31912 0.30976 -0.33187 N 3.76894 -1.94623 -0.02985 N -0.62648 2.31799 1.11595 C 0.51762 4.66433 -0.79103 H 0.07153 5.27058 -0.00712 C -1.02405 -4.66881 -2.07561 H -1.62449 -5.53130 -1.79742 C 2.18321 3.06977 -1.50212 C 1.64227 3.89579 -0.49765 C 0.95648 -3.32197 -1.77031 C 1.67245 3.11395 -2.80629 C 3.03884 -0.56849 4.20611 H 3.05114 -0.61664 5.28360 C 0.47225 -0.41165 3.71137 C 2.24879 -3.06122 -1.10663 C 0.50648 -2.44661 -2.77789 C 0.18632 -4.44811 -1.41929 C 4.11660 -0.65452 3.34149 H 5.17146 -0.78104 3.53147 C 0.56582 3.92722 -3.06961 H 0.15908 3.95627 -4.07650 C -0.34123 -1.49392 3.31462 C -0.72276 -2.69248 -3.38854 H -1.07783 -2.00193 -4.14471 C -0.08598 0.67490 4.40397 C -1.50759 -3.79128 -3.04557 C 3.29995 2.17103 -1.13401 C -1.45913 0.67527 4.66611 H -1.89482 1.52508 5.18616 C -2.28264 -0.37809 4.27168 C 3.40143 -3.86982 -1.06274 H 3.53062 -4.84815 -1.49712 C -1.70392 -1.45534 3.59773 H -2.33536 -2.27352 3.26482 C 0.62819 -5.39089 -0.32415 H 1.45829 -6.02795 -0.64191 H -0.18888 -6.04973 -0.02099 H 0.97241 -4.84466 0.55729 C 2.30622 2.28939 -3.89994




S42

H 2.26252 1.22426 -3.66591 H 3.36377 2.53705 -4.02158 H 1.81369 2.44986 -4.86140 C 5.26393 1.29729 -0.61840 H 6.29881 1.03749 -0.45662 C 2.31021 3.98013 0.85272 H 1.73783 4.59897 1.54440 H 3.30979 4.41428 0.75216 H 2.44402 2.99533 1.30359 C -1.29885 5.47673 -2.33596 H -1.59127 5.43287 -3.38743 H -1.16765 6.52954 -2.06766 H -2.13267 5.09306 -1.73961 C 4.33672 -3.11967 -0.37350 H 5.36157 -3.33019 -0.10957 B 4.40088 -0.75601 0.73601 H 5.56002 -0.98626 0.94930 C -2.87053 -3.99370 -3.65676 H -3.64557 -3.57851 -3.00276 H -3.09834 -5.05340 -3.79929 H -2.95792 -3.49389 -4.62384 C 0.77013 1.82839 4.87038 H 0.16253 2.71334 5.07250 H 1.52441 2.09621 4.12997 H 1.30301 1.57597 5.79300 C 4.68553 2.36919 -1.27601 H 5.18163 3.19157 -1.76736 C 1.33074 -1.26056 -3.21373 H 1.29183 -0.46032 -2.47249 H 0.96206 -0.85663 -4.15671 H 2.38512 -1.52263 -3.32782 C -3.76445 -0.36859 4.55968 H -4.11490 0.62537 4.84896 H -4.01204 -1.05396 5.37719 H -4.33789 -0.68968 3.68589 C 0.23925 -2.66911 2.56713 H 0.49993 -2.39101 1.54431 H -0.47171 -3.49465 2.52034 H 1.16171 -3.02480 3.03289 C -0.04861 4.67670 -2.06856 C -3.10563 1.53957 0.14228 C -4.48029 3.80804 1.08859 C -3.34986 1.71915 1.51403 C -3.55946 2.51914 -0.74143 C -4.24490 3.64153 -0.27177 C -4.02724 2.83696 1.98208 H -2.98355 0.98392 2.21800 H -3.38253 2.41852 -1.80366 H -4.59324 4.38630 -0.98036 H -4.19420 2.95147 3.04845 H -5.00981 4.68327 1.45109 C -2.90757 -1.01467 0.18122 C -3.93132 -3.47667 1.07712 C -4.19690 -1.10363 0.71431 C -2.15329 -2.18846 0.06649 C -2.65507 -3.40152 0.52211 C -4.70616 -2.32411 1.15690 H -4.81705 -0.21985 0.78483 H -1.17104 -2.16083 -0.39009 H -2.04198 -4.28946 0.43893 H -5.71006 -2.36619 1.56761 H -4.31867 -4.42551 1.43437

C -2.19581 0.28576 -1.85576 C -2.21966 0.46309 -4.65967 C -1.19578 0.98561 -2.53107 C -3.20397 -0.33399 -2.60618 C -3.22211 -0.23993 -3.99362 C -1.20547 1.06612 -3.92196 H -0.41103 1.48124 -1.97464 H -3.98824 -0.88347 -2.10036 H -4.01594 -0.72399 -4.55331 H -0.41341 1.60559 -4.42519 H -2.22474 0.53237 -5.74286 MesTpCu-π-complex B3LYP/6-311G(d) 121 opt-MsTpCu-picomp.out Energy: -2918936.0906737 Cu 1.63424 -0.53121 -0.25850 S -1.50250 -0.61604 0.66858 O 0.76393 0.63754 0.90926 N 3.25013 -1.12671 0.82325 N 2.98617 1.04936 -1.33743 N 4.37945 -1.29874 0.08748 N 1.95036 -1.81726 -1.74956 C 3.56934 -1.35237 2.10969 N 4.13778 0.44750 -1.73492 C -3.04803 0.50836 0.53350 N 3.26846 -1.90879 -2.09383 N -0.14077 0.49074 0.05029 C 1.15084 5.27392 -0.31582 H 1.28486 6.04968 0.43438 C -2.06199 -3.99187 -1.28285 H -2.47711 -4.48631 -0.40866 C 1.99533 3.32125 -1.46267 C 2.16000 4.32248 -0.48855 C -0.17223 -2.99236 -2.40763 C -6.15709 -2.34701 1.64329 H -6.92922 -3.05598 1.92475 C -4.15378 -0.50072 0.91090 C 0.82478 3.28692 -2.24559 C 4.93492 -1.67845 2.19667 H 5.49004 -1.91351 3.09112 C 2.58505 -1.25819 3.21897 C -5.27961 -0.69890 0.10520 H -5.39156 -0.14066 -0.81467 C 1.28540 -2.72650 -2.48898 C -6.27294 -1.60785 0.47062 H -7.13970 -1.73459 -0.17053 C -0.99390 -2.69779 -3.51228 C -0.71251 -3.64559 -1.28182 C -2.90866 1.65665 1.54850 C -3.97597 2.24050 -1.07514 H -4.32287 2.80021 -0.21515 C 5.40371 -1.63021 0.89588 H 6.38810 -1.80476 0.48953 C -3.24988 1.05618 -0.88868 C -0.15888 4.25427 -2.03835 H -1.06165 4.22095 -2.64257 C -2.82800 0.35633 -2.02259 H -2.27312 -0.56551 -1.90850 C 1.98593 -2.42658 3.72176 C -2.34077 -3.06804 -3.47068 H -2.97489 -2.83572 -4.32224




S43

C 2.29466 -0.00709 3.79898 C -2.89473 -3.71778 -2.36932 C -1.75922 3.68330 2.24787 H -0.96428 4.40279 2.08159 C 3.07888 2.33358 -1.70492 C -1.90594 2.62120 1.36388 H -1.23785 2.54820 0.51484 C -3.83802 2.00599 -3.47534 H -4.06114 2.37196 -4.47271 C 1.38674 0.05013 4.85491 H 1.15592 1.01691 5.29499 C 0.76256 -1.09323 5.35708 C -2.62362 3.82162 3.33410 H -2.50965 4.65146 4.02460 C 2.19326 -3.40440 -3.32066 H 1.96604 -4.19534 -4.01750 C 1.07995 -2.32120 4.78046 H 0.61189 -3.22497 5.16235 C 0.15154 -3.99861 -0.09533 H 0.92646 -4.72203 -0.36965 H -0.44428 -4.43033 0.70997 H 0.66987 -3.12597 0.30631 C -4.05274 -1.25023 2.09617 H -3.19972 -1.10842 2.74879 C 0.62875 2.23124 -3.30708 H 0.53387 1.23822 -2.86217 H 1.47823 2.19363 -3.99536 H -0.27552 2.42455 -3.88653 C 4.94999 1.33791 -2.34724 H 5.91244 1.03556 -2.73145 C 3.40298 4.38881 0.36866 H 3.27583 5.10255 1.18562 H 4.27922 4.69996 -0.20820 H 3.64402 3.41598 0.80334 C -5.03882 -2.16361 2.45482 H -4.93351 -2.72910 3.37535 C -1.10540 6.28137 -0.86495 H -1.52398 6.62684 -1.81425 H -0.73554 7.15645 -0.32524 H -1.93242 5.86136 -0.28240 C 3.42793 -2.85559 -3.03522 H 4.40827 -3.07107 -3.43059 B 4.38491 -1.04189 -1.44300 H 5.44483 -1.37619 -1.89549 C -3.78099 1.81908 2.63003 H -4.59104 1.11943 2.78743 C -4.26885 2.71003 -2.35375 H -4.83513 3.62905 -2.46899 C -4.35296 -4.10351 -2.33600 H -4.87843 -3.58632 -1.52770 H -4.47769 -5.17774 -2.16696 H -4.85541 -3.85434 -3.27312 C 2.94793 1.25859 3.29896 H 2.70462 2.10370 3.94591 H 2.61291 1.50609 2.28950 H 4.03692 1.16376 3.26310 C 4.31341 2.56294 -2.35161 H 4.67113 3.49138 -2.76908 C -0.45357 -1.99278 -4.73582 H 0.14447 -1.11819 -4.46921 H -1.26766 -1.66174 -5.38420 H 0.19163 -2.64459 -5.33196

C -3.63882 2.88985 3.51435 H -4.33245 2.99042 4.34355 C -0.23264 -0.99028 6.48742 H -1.13175 -0.44937 6.17460 H 0.18510 -0.44875 7.34160 H -0.54508 -1.97585 6.83967 C 2.31647 -3.78679 3.15195 H 2.24555 -3.80086 2.06241 H 1.63968 -4.54923 3.54311 H 3.33748 -4.09086 3.40343 C -0.01559 5.25887 -1.07962 C -3.11668 0.82763 -3.30116 H -2.77166 0.26661 -4.16341 B3LYP-D3/6-311G(d) 121 optD3-MsTpCu-picomp.out Energy: -2919066.0133625 Cu 1.78285 -0.28232 0.21385 S -1.34956 -0.05693 0.91792 O 0.72945 1.23877 0.05156 N 3.02324 0.17631 1.76474 N 3.32138 0.33090 -1.16743 N 4.31696 -0.20778 1.64287 N 2.45910 -2.13553 0.12202 C 2.89943 0.86706 2.90352 N 4.56923 -0.09608 -0.86845 C -2.91357 0.37697 -0.07646 N 3.81617 -2.23677 0.23721 N -0.07778 0.36360 -0.35106 C 0.73544 3.60708 -3.20236 H 0.57535 4.68191 -3.16193 C -1.69208 -3.75535 0.85743 H -2.36084 -3.54674 1.68696 C 2.15734 1.69713 -2.79993 C 1.94759 3.08670 -2.74614 C 0.51886 -3.65994 -0.10651 C -5.90117 -1.81219 2.21252 H -6.63654 -2.36350 2.78970 C -3.99150 -0.38654 0.71060 C 1.14859 0.85017 -3.29655 C 4.15204 0.93037 3.54062 H 4.38499 1.41211 4.47703 C 1.56276 1.39033 3.27586 C -4.87383 -1.27227 0.08992 H -4.82156 -1.42529 -0.97977 C 1.96690 -3.37902 0.01618 C -5.82236 -1.97514 0.83368 H -6.49571 -2.65853 0.32627 C 0.01734 -4.21487 -1.30182 C -0.33918 -3.42887 0.98160 C -3.06707 1.90503 -0.01046 C -3.58608 0.56028 -2.51156 H -4.14760 1.44856 -2.24871 C 5.01734 0.23755 2.70548 H 6.07342 0.03228 2.79176 C -2.83397 -0.10064 -1.53265 C -0.05019 1.41078 -3.73881 H -0.83362 0.75454 -4.10284 C -2.12089 -1.24345 -1.90235 H -1.53000 -1.76952 -1.16658 C 0.74162 0.64875 4.13946 C -1.33309 -4.54741 -1.37327




S44

H -1.72487 -4.97118 -2.29444 C 1.08893 2.57575 2.68264 C -2.20639 -4.32080 -0.30650 C -2.17595 4.09756 -0.56383 H -1.39991 4.69002 -1.03766 C 3.40081 1.11008 -2.24714 C -2.09254 2.71312 -0.61626 H -1.26919 2.25876 -1.14905 C -2.92081 -1.05693 -4.17660 H -2.94823 -1.42456 -5.19753 C -0.21235 2.98877 2.95561 H -0.59674 3.88064 2.46824 C -1.05117 2.26425 3.80431 C -3.24803 4.71541 0.08242 H -3.31349 5.79790 0.12637 C 3.02640 -4.30197 0.06135 H 2.95231 -5.37640 0.00951 C -0.55559 1.10242 4.39207 H -1.19727 0.52220 5.05051 C 0.18374 -2.85055 2.27266 H 0.94586 -3.49884 2.71623 H -0.61753 -2.71207 2.99870 H 0.65455 -1.87951 2.11895 C -4.08747 -0.22214 2.10328 H -3.42396 0.47095 2.60669 C 1.31746 -0.65020 -3.33256 H 1.06718 -1.08908 -2.36392 H 2.34398 -0.94241 -3.56212 H 0.65168 -1.09938 -4.07127 C 5.45093 0.41283 -1.75780 H 6.50318 0.18297 -1.68635 C 2.99703 4.00782 -2.17037 H 2.61829 5.02798 -2.07823 H 3.89622 4.04134 -2.79214 H 3.31461 3.67434 -1.17892 C -5.02623 -0.92897 2.84552 H -5.07653 -0.78562 3.92033 C -1.59503 3.35787 -4.16227 H -1.97153 2.83319 -5.04393 H -1.51167 4.41922 -4.40911 H -2.35488 3.25987 -3.38082 C 4.16954 -3.53495 0.20158 H 5.20763 -3.81809 0.27995 B 4.75356 -0.99325 0.37619 H 5.89207 -1.35480 0.48034 C -4.15231 2.53321 0.60530 H -4.94268 1.94270 1.05005 C -3.63275 0.08605 -3.82067 H -4.22367 0.61595 -4.56089 C -3.67226 -4.64257 -0.44590 H -4.21810 -4.44984 0.47854 H -3.82588 -5.68998 -0.72352 H -4.12779 -4.02798 -1.22875 C 1.97095 3.38157 1.76072 H 1.41203 4.19383 1.29284 H 2.38664 2.76345 0.96453 H 2.81513 3.81706 2.30514 C 4.74825 1.19442 -2.66108 H 5.14256 1.73500 -3.50719 C 0.91582 -4.42987 -2.49691 H 1.50504 -3.53653 -2.71713 H 0.33312 -4.67953 -3.38612

H 1.62835 -5.24218 -2.32915 C -4.24024 3.92662 0.65360 H -5.09260 4.38930 1.14132 C -2.46055 2.73801 4.05807 H -2.98535 2.92689 3.11796 H -2.46721 3.67605 4.62298 H -3.03786 2.00750 4.63055 C 1.25122 -0.61281 4.79520 H 1.77779 -1.25355 4.08590 H 0.43478 -1.19131 5.23231 H 1.96169 -0.38159 5.59531 C -0.27613 2.78607 -3.70385 C -2.16292 -1.71534 -3.21050 H -1.59229 -2.60015 -3.46847 MesTpCu- S(CPh3)/NO B3LYP/6-311G(d) 121 opt-MsTpCu-NO-SCPh3.out Energy: -2918940.1873565 Cu 0.98965 0.04662 0.99031 S -1.04383 0.49709 -0.12474 O 1.24632 1.11900 -1.69165 N 0.75528 -1.14854 2.70366 N 3.06425 -0.07263 1.03576 N 1.64191 -0.79078 3.67503 N 0.93974 1.89669 2.35176 C 0.01985 -2.15537 3.20969 N 3.53586 0.16426 2.29425 C -1.83011 -0.19551 -1.74212 N 1.82427 1.71335 3.36743 N 0.84123 1.34359 -0.62150 C 4.13751 -2.14453 -3.00563 H 4.14324 -3.18120 -3.33394 C -2.86464 4.14574 0.96014 H -3.92443 3.95900 1.11522 C 4.10106 -0.52752 -1.21037 C 4.09896 -1.87005 -1.63798 C -0.56679 3.73939 1.58776 C -6.07954 -0.22871 -0.77181 H -7.13644 -0.24622 -0.52490 C -3.33474 -0.17416 -1.40573 C 4.19048 0.51164 -2.15376 C 0.44727 -2.44672 4.51892 H 0.05831 -3.21156 5.17246 C -1.06922 -2.86996 2.49697 C -4.27242 0.47011 -2.21824 H -3.95043 0.99626 -3.10694 C 0.43920 3.13199 2.50023 C -5.63222 0.44200 -1.90410 H -6.33887 0.95001 -2.55300 C -0.14340 4.61295 0.56994 C -1.94044 3.50269 1.78455 C -1.34370 -1.61117 -2.07363 C -1.19114 0.33359 -4.16908 H -1.12115 -0.72812 -4.36614 C 1.47262 -1.55786 4.76875 H 2.09180 -1.41285 5.64039 C -1.49945 0.79004 -2.88342 C 4.21709 0.19124 -3.51313 H 4.26718 0.99791 -4.23988 C -1.58908 2.17517 -2.68055 H -1.82742 2.56260 -1.69757




S45

C -2.40442 -2.68600 2.90661 C -1.10204 5.23595 -0.23354 H -0.76962 5.91373 -1.01602 C -0.76118 -3.82607 1.51184 C -2.46785 5.01804 -0.05445 C 0.47853 -3.15385 -2.52805 H 1.54521 -3.34447 -2.55435 C 4.14537 -0.22272 0.24415 C 0.02440 -1.90739 -2.11101 H 0.75019 -1.14821 -1.84771 C -1.05428 2.59950 -4.99927 H -0.87763 3.29681 -5.81222 C -1.79316 -4.57557 0.94568 H -1.55029 -5.30708 0.18024 C -3.12176 -4.41409 1.33765 C -0.42614 -4.13886 -2.92146 H -0.07110 -5.11046 -3.25092 C 1.00982 3.75051 3.63287 H 0.79969 4.73923 4.01042 C -3.40429 -3.46530 2.32065 H -4.43293 -3.32822 2.64568 C -2.42461 2.55256 2.85190 H -1.90821 2.70700 3.80219 H -3.49746 2.66555 3.02153 H -2.24386 1.51659 2.55094 C -3.80053 -0.85650 -0.27154 H -3.10026 -1.38282 0.36620 C 4.30438 1.95566 -1.72658 H 3.68623 2.17920 -0.85709 H 5.33660 2.20201 -1.45436 H 4.00692 2.62706 -2.53439 C 4.88119 0.16457 2.29363 H 5.42767 0.33408 3.20831 C 4.11206 -3.00530 -0.64126 H 3.98538 -3.96879 -1.13940 H 5.05944 -3.03793 -0.09396 H 3.32505 -2.90533 0.10798 C -5.15410 -0.88221 0.04222 H -5.48463 -1.41561 0.92745 C 4.17176 -1.45005 -5.43550 H 4.63537 -0.65565 -6.02502 H 4.70395 -2.38071 -5.64886 H 3.14679 -1.57174 -5.80286 C 1.88129 2.81290 4.14938 H 2.53277 2.84514 5.00935 B 2.61358 0.39999 3.51900 H 3.30210 0.46803 4.50019 C -2.24085 -2.60673 -2.47682 H -3.30430 -2.40604 -2.48024 C -0.97217 1.22893 -5.21637 H -0.73306 0.84518 -6.20333 C -3.49134 5.68681 -0.94068 H -3.91871 4.97892 -1.65928 H -4.32350 6.09150 -0.35774 H -3.05345 6.50944 -1.51080 C 0.66740 -4.06738 1.09065 H 0.72996 -4.86877 0.35314 H 1.10691 -3.17239 0.64631 H 1.29437 -4.33800 1.94569 C 5.31712 -0.07701 1.00577 H 6.33320 -0.15023 0.65121 C 1.32399 4.88350 0.33600

H 1.87837 3.95250 0.19589 H 1.47233 5.50344 -0.55070 H 1.78226 5.39819 1.18562 C -1.78765 -3.85804 -2.89443 H -2.50751 -4.60930 -3.20439 C -4.22512 -5.21859 0.69530 H -4.64045 -4.69347 -0.17188 H -3.86372 -6.18835 0.34474 H -5.04931 -5.39903 1.39010 C -2.77067 -1.67736 3.97102 H -2.27936 -0.71660 3.80357 H -3.84913 -1.50704 3.99188 H -2.47085 -2.01311 4.96830 C 4.18241 -1.12762 -3.96134 C -1.36456 3.06725 -3.72302 H -1.42919 4.13357 -3.53146 B3LYP-D3/6-311G(d) 121 optD3-MsTpCu-NO-SCPh3.out Energy: -2919070.2899995 Cu 1.18726 -0.82795 -0.10469 S -0.88700 -0.11253 0.58757 O 1.08798 1.88784 1.03797 N 1.07959 -2.63784 -1.17364 N 3.17443 -0.59716 -0.50713 N 2.12095 -3.47736 -0.92982 N 1.63533 -2.12578 1.68446 C 0.21291 -3.30686 -1.95052 N 3.89482 -1.75133 -0.41268 C -1.94403 1.36936 -0.01251 N 2.68536 -2.95486 1.45763 N 0.94519 0.76273 1.28617 C 2.86088 3.63965 -2.29600 H 2.57509 4.04153 -3.26424 C -2.25815 -1.34303 3.80648 H -3.26275 -1.68141 3.56705 C 3.63104 1.79455 -0.95064 C 3.27586 2.31015 -2.20731 C 0.13071 -1.56313 3.55032 C -5.98518 -0.14490 0.54601 H -6.99099 -0.53171 0.67604 C -3.37421 0.85122 0.22455 C 3.63093 2.62126 0.18572 C 0.70650 -4.60102 -2.20600 H 0.24732 -5.36340 -2.81461 C -1.01382 -2.68894 -2.49343 C -4.32810 1.57176 0.94666 H -4.07083 2.52706 1.38479 C 1.29490 -2.27210 2.96921 C -5.62335 1.07511 1.10742 H -6.34798 1.65119 1.67434 C 0.32161 -0.43400 4.36152 C -1.16745 -2.02429 3.26834 C -1.71561 1.71363 -1.48454 C -1.36081 3.84597 0.36529 H -1.35686 4.00658 -0.70438 C 1.91555 -4.66155 -1.53972 H 2.64295 -5.45397 -1.45492 C -1.62019 2.57632 0.88637 C 3.20189 3.94118 0.05601 H 3.16007 4.57096 0.94055




S46

C -1.61649 2.41932 2.27878 H -1.80616 1.44364 2.70324 C -2.27666 -3.25631 -2.23787 C -0.79618 0.21138 4.89479 H -0.64912 1.08869 5.51971 C -0.90181 -1.56373 -3.33121 C -2.09369 -0.22422 4.62452 C -0.22190 2.29387 -3.30188 H 0.78712 2.37199 -3.68265 C 4.04501 0.37977 -0.81505 C -0.42476 1.82930 -2.00733 H 0.43277 1.56138 -1.40153 C -1.07601 4.75056 2.59046 H -0.85848 5.58771 3.24624 C -2.05773 -0.99794 -3.86618 H -1.96988 -0.11045 -4.48338 C -3.32006 -1.53556 -3.61829 C -1.30299 2.65526 -4.10267 H -1.13892 3.01640 -5.11304 C 2.14822 -3.20896 3.58842 H 2.11547 -3.54325 4.61365 C -3.40497 -2.67672 -2.82029 H -4.38128 -3.11140 -2.62048 C -1.38297 -3.20312 2.35227 H -0.76873 -4.05939 2.64316 H -2.42966 -3.51359 2.34536 H -1.10262 -2.94629 1.32775 C -3.75447 -0.36953 -0.34813 H -3.03726 -0.93209 -0.93030 C 4.07394 2.08386 1.52442 H 3.60821 1.12144 1.74554 H 5.15580 1.91930 1.54228 H 3.82210 2.77438 2.33113 C 5.19322 -1.50367 -0.66417 H 5.91678 -2.30323 -0.63059 C 3.35665 1.43823 -3.43729 H 3.07134 1.98590 -4.33797 H 4.37073 1.05736 -3.58519 H 2.70829 0.56447 -3.35020 C -5.04240 -0.86367 -0.19022 H -5.30593 -1.81261 -0.64519 C 2.24295 5.86341 -1.26510 H 2.77799 6.55292 -0.60682 H 2.29981 6.25546 -2.28329 H 1.18962 5.87982 -0.96427 C 3.01227 -3.61722 2.58810 H 3.82394 -4.32869 2.59444 B 3.26419 -3.09476 0.03577 H 4.10861 -3.94801 0.02092 C -2.79555 2.07768 -2.29684 H -3.80461 2.00879 -1.91129 C -1.09086 4.92283 1.21057 H -0.88811 5.89869 0.78027 C -3.29576 0.52761 5.14114 H -3.76575 1.10675 4.33846 H -4.05722 -0.15191 5.53359 H -3.02602 1.22542 5.93746 C 0.45073 -0.99211 -3.67517 H 0.37211 -0.23396 -4.45394 H 0.91395 -0.52817 -2.80373 H 1.13744 -1.77341 -4.01196 C 5.33863 -0.15340 -0.92942

H 6.24252 0.38487 -1.16689 C 1.71007 0.09557 4.62451 H 2.22376 0.30965 3.68390 H 1.68033 1.01562 5.21202 H 2.32650 -0.63076 5.16126 C -2.59354 2.54270 -3.59413 H -3.44919 2.81500 -4.20389 C -4.56485 -0.86077 -4.13474 H -4.97187 -0.18443 -3.37465 H -4.36143 -0.26492 -5.02734 H -5.34716 -1.58412 -4.37957 C -2.43392 -4.46375 -1.34315 H -1.79302 -4.39914 -0.46212 H -3.46708 -4.56645 -1.00405 H -2.16506 -5.38934 -1.86134 C 2.79147 4.46176 -1.17094 C -1.34327 3.48841 3.12109 H -1.33478 3.32938 4.19463 TS (B3LYP/6-311G(d)) 121 ts-MsTpCu-ONSCPh3.out Energy: -2918934.9006656 Cu 1.31467 -0.28935 0.71714 S -1.23756 -0.49961 0.01087 O 0.62586 -0.87342 -1.98155 N 1.29249 -2.07736 2.08748 N 3.31526 -0.61767 0.08710 N 2.48064 -2.12288 2.75043 N 1.92980 0.93802 2.26864 C 0.63584 -3.20357 2.40476 N 4.09159 -0.95523 1.15393 C -2.49142 0.44185 -1.11702 N 2.94021 0.36247 2.98013 N 0.40397 -1.13013 -0.84813 C 3.17356 -0.98732 -4.64677 H 3.10001 -1.76855 -5.39923 C -1.63980 3.84657 2.32203 H -2.68404 3.68135 2.56876 C 3.64599 -0.32989 -2.37125 C 3.56011 -1.33561 -3.35068 C 0.65283 3.08664 2.36835 C -5.44094 2.11676 1.61556 H -6.19630 2.52175 2.28154 C -3.48448 1.06471 -0.11812 C 3.34746 1.00495 -2.70606 C 1.41279 -3.98455 3.28447 H 1.15059 -4.93873 3.71473 C -0.71391 -3.53782 1.87849 C -3.93869 2.37899 -0.26169 H -3.54113 3.00498 -1.04991 C 1.68410 2.12961 2.84195 C -4.91236 2.89719 0.59281 H -5.25439 3.91779 0.45288 C 1.04727 4.25608 1.68771 C -0.70058 2.88235 2.69383 C -3.18705 -0.61400 -1.99585 C -2.06651 1.70354 -3.30154 H -2.78124 1.05854 -3.79605 C 2.57240 -3.25915 3.47341 H 3.45071 -3.46596 4.06570 C -1.76443 1.50723 -1.94989 C 2.96549 1.30800 -4.01189




S47

H 2.73219 2.33903 -4.26489 C -0.84799 2.37764 -1.34476 H -0.60947 2.26575 -0.29386 C -1.85966 -3.20219 2.61964 C 0.07507 5.19367 1.33631 H 0.38103 6.09605 0.81217 C -0.84074 -4.23644 0.66223 C -1.27367 5.00857 1.64367 C -3.04061 -2.41057 -3.62875 H -2.42605 -3.07192 -4.23133 C 4.10489 -0.66632 -0.99980 C -2.42880 -1.48362 -2.79300 H -1.34879 -1.42111 -2.78213 C -0.54864 3.58033 -3.41900 H -0.07795 4.37792 -3.98522 C -2.11426 -4.56630 0.20046 H -2.21048 -5.09795 -0.74296 C -3.26738 -4.23244 0.91297 C -4.43132 -2.48930 -3.69699 H -4.90938 -3.21303 -4.34949 C 2.54483 2.31663 3.93846 H 2.58162 3.16922 4.59819 C -3.11712 -3.55639 2.12290 H -4.00168 -3.30154 2.70195 C -1.13537 1.66395 3.47201 H -0.75181 1.69511 4.49741 H -2.22305 1.59583 3.51936 H -0.75850 0.74455 3.02199 C -4.03370 0.28280 0.91148 H -3.71859 -0.74772 1.03167 C 3.44280 2.10442 -1.67590 H 2.71133 1.96631 -0.87584 H 4.42708 2.12426 -1.19880 H 3.26471 3.08161 -2.12844 C 5.35126 -1.21098 0.74710 H 6.11127 -1.49093 1.46016 C 3.84884 -2.78277 -3.02473 H 3.55845 -3.43238 -3.85315 H 4.91026 -2.95698 -2.82567 H 3.30568 -3.10902 -2.13419 C -4.99343 0.80498 1.77182 H -5.39975 0.18000 2.56077 C 2.42272 0.67993 -6.39640 H 1.35009 0.90016 -6.42319 H 2.94199 1.56618 -6.77274 H 2.60767 -0.13717 -7.09734 C 3.32001 1.17421 3.98468 H 4.11184 0.88044 4.65620 B 3.54330 -1.01393 2.60364 H 4.45617 -1.25074 3.34676 C -4.58118 -0.69596 -2.08210 H -5.20260 -0.03131 -1.49665 C -1.46258 2.72880 -4.02967 H -1.71419 2.85757 -5.07777 C -2.30563 6.02770 1.22651 H -1.92518 7.04813 1.32257 H -2.59506 5.88875 0.17892 H -3.21329 5.95012 1.82896 C 0.37840 -4.62554 -0.13940 H 0.09588 -5.15827 -1.04984 H 0.95978 -3.74621 -0.42782 H 1.04856 -5.27144 0.43535

C 5.40898 -1.04075 -0.62186 H 6.26723 -1.14897 -1.26629 C 2.49759 4.52092 1.35514 H 2.98201 3.64380 0.92194 H 2.59127 5.34623 0.64595 H 3.07273 4.78729 2.24709 C -5.19667 -1.62375 -2.92384 H -6.28054 -1.66254 -2.97032 C -4.63260 -4.58557 0.37446 H -4.68738 -5.63771 0.07906 H -5.41552 -4.40746 1.11531 H -4.87254 -3.98929 -0.51180 C -1.74913 -2.46100 3.93085 H -1.29114 -1.47798 3.79323 H -2.73220 -2.31318 4.38308 H -1.12483 -2.99859 4.64956 C 2.86949 0.32609 -4.99871 C -0.24623 3.40019 -2.06988 H 0.45624 4.05864 -1.57121 iPr2TpCu-SCPh3 B3LYP/6-311G(d) 116 opt-iPr2TpCu-SCPh3.out Energy: -2624426.5369673 Cu -0.07940 -0.06418 0.11244 S 1.88293 -0.19729 1.04943 N -1.13233 1.50252 -0.56276 N -2.48081 1.31134 -0.68668 N -1.53793 -0.27677 1.80436 N -2.83134 -0.16003 1.37196 N -1.15527 -1.41128 -0.90734 N -2.50927 -1.22878 -0.90416 C 0.99202 3.85767 -2.24547 C 0.59863 4.45433 0.18932 C 0.52725 3.34328 -0.87332 C -0.85729 2.75790 -0.93818 C -2.04717 3.38831 -1.32672 C -3.05693 2.45049 -1.15524 C -4.52264 2.61018 -1.47365 C -4.76318 2.50610 -2.99219 C -5.07720 3.93550 -0.92569 C -0.39305 -1.79939 4.89816 C -0.02013 0.70409 4.72002 C -0.32235 -0.59327 3.94874 C -1.57731 -0.45367 3.12609 C -2.91508 -0.45698 3.56385 C -3.68733 -0.27057 2.42752 C -5.18752 -0.15096 2.31916 C -5.90383 -1.01763 3.36540 C -5.63400 1.31947 2.43131 C 0.70727 -3.94505 -2.85871 C 0.78539 -4.06571 -0.32748 C 0.48834 -3.17472 -1.54893 C -0.90268 -2.60593 -1.45705 C -2.11682 -3.20354 -1.82529 C -3.11547 -2.31209 -1.45482 C -4.60714 -2.44525 -1.63832 C -5.06263 -1.80541 -2.96316 C -5.05660 -3.91169 -1.55830 C 3.49584 -0.00242 0.05581 C 3.31984 -0.44271 -1.40935




S48

C 2.29642 0.10383 -2.19609 C 2.16159 -0.21781 -3.54115 C 3.05652 -1.10162 -4.14423 C 4.07970 -1.65170 -3.38115 C 4.21206 -1.32402 -2.02986 C 4.52794 -0.89378 0.78116 C 4.18969 -2.20341 1.15033 C 5.11807 -3.04383 1.75357 C 6.41399 -2.59435 2.00602 C 6.76464 -1.29879 1.64360 C 5.83122 -0.45721 1.03563 C 3.91370 1.48133 0.14004 C 4.51068 2.13632 -0.94283 C 4.97101 3.44913 -0.82542 C 4.84565 4.13352 0.37882 C 4.25523 3.49109 1.46691 C 3.79575 2.18400 1.34849 B -3.11659 -0.00852 -0.14924 H -4.29014 0.02374 -0.33970 H 0.35868 4.67751 -2.59786 H 2.01839 4.22793 -2.18561 H 0.96338 3.06831 -3.00075 H 0.29862 4.07930 1.17062 H 1.61901 4.83639 0.27138 H -0.05956 5.29045 -0.06612 H 1.20755 2.54892 -0.55597 H -2.15841 4.40002 -1.68429 H -5.06784 1.79533 -0.99397 H -5.83146 2.57150 -3.21961 H -4.25519 3.31487 -3.52509 H -4.38987 1.56114 -3.39317 H -6.15257 4.00458 -1.11253 H -4.91438 4.02563 0.15063 H -4.60538 4.79727 -1.40624 H -0.58685 -2.72581 4.35154 H 0.55082 -1.91771 5.43815 H -1.18566 -1.68068 5.64380 H -0.81621 0.93634 5.43446 H 0.91689 0.61295 5.27778 H 0.07552 1.55147 4.03689 H 0.50518 -0.76110 3.25385 H -3.27113 -0.58557 4.57400 H -5.48671 -0.51332 1.33157 H -5.59819 -2.06428 3.29664 H -5.69529 -0.67442 4.38268 H -6.98709 -0.97011 3.22203 H -6.71738 1.40936 2.30360 H -5.37397 1.72910 3.41156 H -5.15089 1.94135 1.67478 H 0.50392 -3.31804 -3.72958 H 1.74240 -4.28835 -2.92842 H 0.06271 -4.82765 -2.91905 H 1.80982 -4.44741 -0.37103 H 0.66937 -3.50832 0.60493 H 0.10765 -4.92409 -0.29198 H 1.18843 -2.33583 -1.52973 H -2.24994 -4.16412 -2.29622 H -5.09663 -1.90594 -0.82309 H -6.14892 -1.87663 -3.07451 H -4.78731 -0.75015 -3.01177 H -4.60199 -2.31044 -3.81712 H -4.65078 -4.50365 -2.38367

H -4.73947 -4.37839 -0.62290 H -6.14649 -3.97716 -1.61714 H 1.59201 0.79043 -1.74765 H 1.35164 0.21941 -4.11640 H 2.95379 -1.35696 -5.19401 H 4.78779 -2.33960 -3.83283 H 5.02609 -1.75774 -1.46412 H 3.18181 -2.55831 0.97355 H 4.82550 -4.05104 2.03387 H 7.13830 -3.24702 2.48310 H 7.76806 -0.93117 1.83505 H 6.13111 0.54631 0.76129 H 4.63098 1.62184 -1.88778 H 5.43219 3.93067 -1.68224 H 5.20428 5.15382 0.47160 H 4.15087 4.00989 2.41479 H 3.33768 1.69856 2.20086 B3LYP-D3/6-311G(d) 116 optD3-iPr2TpCu-SCPh3.out Energy: -2624541.7135083 Cu -0.02592 -0.11295 0.22627 S 1.91062 -0.14028 1.18461 N -1.05955 1.46805 -0.44498 N -2.39860 1.29369 -0.65689 N -1.54317 -0.29028 1.82369 N -2.82270 -0.19805 1.35439 N -1.08840 -1.41679 -0.84105 N -2.43618 -1.22534 -0.91626 C 1.18337 3.94316 -1.77373 C 0.60511 4.29639 0.67297 C 0.61569 3.30232 -0.49983 C -0.75984 2.74160 -0.71911 C -1.92250 3.40283 -1.14211 C -2.94220 2.46056 -1.08948 C -4.37891 2.62668 -1.50771 C -4.48904 2.61067 -3.04415 C -4.98736 3.91322 -0.92914 C 0.16856 -2.04770 3.88342 C -0.57034 -0.17760 5.42345 C -0.36058 -0.60540 3.96636 C -1.61339 -0.44514 3.14507 C -2.96286 -0.46270 3.54698 C -3.70480 -0.30306 2.38394 C -5.19562 -0.18300 2.20922 C -5.95812 -0.85070 3.36023 C -5.60560 1.29396 2.06493 C 0.83518 -4.15545 -2.49505 C 0.88186 -3.77816 0.01236 C 0.58759 -3.15493 -1.36338 C -0.80961 -2.60510 -1.38577 C -2.00268 -3.19134 -1.83562 C -3.01579 -2.29429 -1.51414 C -4.49654 -2.38839 -1.77332 C -4.91193 -1.46440 -2.93193 C -4.92845 -3.83430 -2.04601 C 3.41263 0.05962 0.03252 C 3.06033 -0.41685 -1.38545 C 2.01888 0.20733 -2.08747 C 1.66140 -0.19487 -3.36650 C 2.35629 -1.22940 -3.99404 C 3.41202 -1.83798 -3.32558




S49

C 3.76273 -1.43501 -2.03457 C 4.53000 -0.80331 0.64990 C 4.24669 -2.09655 1.11128 C 5.25247 -2.91860 1.60554 C 6.57068 -2.46453 1.65419 C 6.86488 -1.18325 1.20055 C 5.85389 -0.36036 0.70173 C 3.82675 1.54324 0.02225 C 4.37303 2.12847 -1.12525 C 4.84372 3.44129 -1.10687 C 4.77789 4.19542 0.06048 C 4.24043 3.62091 1.21178 C 3.77362 2.31094 1.19245 B -3.06934 -0.02377 -0.16891 H -4.23652 0.01471 -0.38981 H 0.56825 4.78899 -2.09620 H 2.19752 4.30503 -1.59573 H 1.22354 3.22668 -2.59806 H 0.24680 3.81501 1.58618 H 1.61375 4.67183 0.85829 H -0.04771 5.14879 0.46179 H 1.26415 2.47382 -0.20658 H -2.00871 4.43413 -1.44596 H -4.94931 1.77889 -1.12380 H -5.53554 2.66909 -3.35802 H -3.95610 3.46089 -3.47920 H -4.05773 1.69984 -3.46507 H -6.04361 3.99239 -1.20090 H -4.91353 3.93704 0.16027 H -4.47930 4.80079 -1.31679 H 0.36557 -2.33134 2.84895 H 1.10460 -2.14942 4.44023 H -0.55785 -2.75375 4.29789 H -1.28604 -0.83209 5.93120 H 0.37108 -0.23112 5.97656 H -0.94666 0.84646 5.49053 H 0.40145 0.04645 3.52498 H -3.34645 -0.57294 4.54841 H -5.47021 -0.69894 1.28299 H -5.67061 -1.89837 3.47652 H -5.76804 -0.34274 4.31017 H -7.03548 -0.81027 3.17800 H -6.67915 1.38657 1.87323 H -5.37409 1.84542 2.98080 H -5.07056 1.77459 1.24513 H 0.61431 -3.71529 -3.46981 H 1.88147 -4.46981 -2.49945 H 0.21870 -5.05220 -2.37577 H 1.90609 -4.16044 0.05006 H 0.76749 -3.03136 0.79989 H 0.19971 -4.60656 0.22428 H 1.26678 -2.31107 -1.49047 H -2.11266 -4.14487 -2.32553 H -5.01614 -2.04850 -0.87080 H -5.99278 -1.50934 -3.09606 H -4.64346 -0.42750 -2.72750 H -4.41477 -1.76429 -3.85905 H -4.48158 -4.21511 -2.96916 H -4.63729 -4.50101 -1.23087 H -6.01399 -3.89115 -2.16023 H 1.48810 1.02966 -1.63308 H 0.83382 0.29657 -3.86737

H 2.07672 -1.55339 -4.99114 H 3.96835 -2.63928 -3.80139 H 4.58758 -1.92708 -1.53677 H 3.22517 -2.45354 1.08448 H 5.00409 -3.91456 1.95893 H 7.35667 -3.10275 2.04536 H 7.88489 -0.81327 1.23497 H 6.10742 0.63278 0.35359 H 4.44034 1.55706 -2.04256 H 5.25935 3.87178 -2.01255 H 5.13924 5.21871 0.07465 H 4.18189 4.19480 2.13121 H 3.35264 1.87715 2.09032 iPr2TpCu-N(O)SCPh3 B3LYP/6-311G(d) 118 opt-iPr2TpCu-K1N-ONSCPh3-syn.out Energy: -2705967.7573264 Cu 0.55606 -0.06155 -0.23428 S -2.38578 0.27466 0.56075 O -1.65685 -0.56405 -1.83872 N 1.53265 1.71197 -0.00987 N 2.11366 -0.75062 -1.58748 N 2.87773 1.61217 0.20477 N 1.56104 -0.96904 1.30136 C 1.22616 3.01138 -0.05890 N 3.37174 -0.52174 -1.10590 C -4.21910 0.03500 0.04977 N 2.88538 -0.64894 1.39020 N -1.21747 -0.23370 -0.76682 C -6.07647 0.25100 3.98528 H -6.53507 0.31598 4.96664 C -4.88319 0.07612 1.44116 C 2.39031 3.77211 0.13392 H 2.47118 4.84771 0.15387 C -5.64951 -0.97816 1.94592 H -5.79673 -1.87290 1.35572 C 1.26607 -1.76214 2.33374 C -6.24407 -0.88788 3.20508 H -6.84070 -1.71697 3.57212 C -4.70224 1.20617 -0.81970 C -5.16636 -1.45973 -1.79827 H -5.65225 -0.59388 -2.22881 C 3.42170 2.85585 0.29517 C -4.37333 -1.32275 -0.65531 C -3.75767 -2.47260 -0.13916 H -3.13506 -2.39645 0.74453 C -4.37614 2.78542 -2.63707 H -3.72723 3.20489 -3.39912 C 2.24274 -1.41587 -2.73655 C -3.89649 1.76915 -1.81505 H -2.89028 1.40366 -1.96768 C -4.72038 -3.83423 -1.88562 H -4.84906 -4.80031 -2.36292 C -5.67723 3.25947 -2.48546 H -6.04974 4.05404 -3.12391 C 2.41696 -1.95893 3.11463 H 2.50275 -2.55095 4.01233 C -4.73519 1.22758 2.23255 H -4.16979 2.07087 1.85156 C 4.29803 -1.04216 -1.95843




S50

C -5.31850 1.31198 3.49107 H -5.18445 2.21064 4.08446 C 3.42736 -1.23816 2.49088 B 3.54404 0.20298 0.26039 H 4.70326 0.33144 0.49913 C -6.01089 1.68662 -0.68215 H -6.66298 1.26603 0.07383 C -5.33867 -2.70327 -2.40612 H -5.95628 -2.77944 -3.29540 C 3.60548 -1.61908 -3.01505 H 4.03194 -2.11367 -3.87326 C -6.49374 2.70177 -1.50619 H -7.51121 3.05655 -1.37571 C -3.92705 -3.71192 -0.74559 H -3.43231 -4.58333 -0.32873 C 1.02557 -1.88437 -3.49326 H 0.27152 -1.09532 -3.41400 C -0.18483 3.48009 -0.28862 H -0.77967 2.58718 -0.50125 C -0.11922 -2.31868 2.52085 H -0.72088 -1.93002 1.69314 C 1.31411 -2.12401 -4.97974 H 2.02867 -2.94057 -5.12467 H 1.72436 -1.23148 -5.45962 H 0.39657 -2.39787 -5.50791 C 0.43502 -3.14175 -2.82822 H 0.22350 -2.95149 -1.77408 H 1.13577 -3.98090 -2.88467 H -0.49919 -3.44009 -3.31270 C -0.28014 4.41334 -1.50669 H 0.11419 3.93355 -2.40601 H 0.28646 5.33565 -1.34705 H -1.32062 4.69236 -1.69739 C -0.77223 4.14356 0.96855 H -0.21639 5.04758 1.23555 H -0.73752 3.46563 1.82470 H -1.81556 4.42855 0.80303 C -0.75411 -1.83502 3.83492 H -0.18840 -2.19066 4.70157 H -1.77903 -2.20534 3.93153 H -0.78603 -0.74404 3.88133 C -0.12431 -3.85451 2.43139 H 0.28967 -4.19792 1.48019 H -1.14319 -4.24439 2.52040 H 0.47071 -4.30114 3.23362 C 4.89493 3.12686 0.47387 H 5.33137 2.28304 1.01418 C 4.85681 -1.04538 2.93293 H 5.47641 -0.93645 2.03872 C 5.78681 -1.01941 -1.71477 H 6.01529 -0.15474 -1.08650 C 6.23998 -2.28076 -0.95432 H 7.31063 -2.23752 -0.73041 H 6.05535 -3.17960 -1.54966 H 5.70020 -2.39322 -0.01138 C 6.57466 -0.86171 -3.02423 H 7.64615 -0.78535 -2.81787 H 6.26991 0.03437 -3.57015 H 6.43077 -1.72045 -3.68610 C 5.14079 4.39168 1.31003 H 6.21143 4.52895 1.48589 H 4.64281 4.33419 2.28092

H 4.77749 5.28881 0.80047 C 5.60464 3.22481 -0.89036 H 6.68096 3.37345 -0.75879 H 5.21559 4.06642 -1.47072 H 5.45694 2.31900 -1.48219 C 5.00662 0.24463 3.76268 H 6.05271 0.40820 4.03980 H 4.41867 0.18437 4.68322 H 4.66255 1.11955 3.20714 C 5.37988 -2.25871 3.71507 H 6.43599 -2.12300 3.96398 H 5.28483 -3.18109 3.13715 H 4.83957 -2.39552 4.65636 B3LYP-D3/6-311G(d) 118 optD3-iPr2TpCu-K1N-ONSCPh3-syn.out Energy: -2706078.7110142 Cu 0.55070 0.05390 -0.37107 S -2.32671 0.58840 0.46028 O -1.72902 -0.50487 -1.85277 N 1.60100 1.77032 -0.33918 N 2.08391 -0.90016 -1.49670 N 2.94763 1.65778 -0.16886 N 1.50670 -0.65697 1.30711 C 1.32837 3.04576 -0.61730 N 3.34823 -0.70366 -1.02481 C -4.09555 0.03184 0.04890 N 2.82181 -0.31627 1.41488 N -1.22820 -0.07977 -0.84177 C -6.01894 0.68335 3.89757 H -6.49317 0.85928 4.85760 C -4.78123 0.22113 1.41538 C 2.52448 3.78332 -0.62791 H 2.64102 4.83817 -0.81795 C -5.38902 -0.82414 2.11360 H -5.39663 -1.82267 1.69732 C 1.13185 -1.20730 2.46066 C -6.00566 -0.59245 3.34393 H -6.47710 -1.41844 3.86685 C -4.74876 0.94996 -0.99268 C -4.61615 -1.86407 -1.59468 H -5.14968 -1.15973 -2.21899 C 3.53462 2.86856 -0.34550 C -4.01680 -1.43307 -0.41045 C -3.30917 -2.37288 0.35458 H -2.83243 -2.06268 1.27549 C -4.66187 2.42604 -2.91559 H -4.07037 2.95834 -3.65351 C 2.13067 -1.90183 -2.37181 C -4.01784 1.64407 -1.95890 H -2.93899 1.57827 -1.97648 C -3.79977 -4.11309 -1.24185 H -3.70649 -5.14334 -1.56952 C -6.05040 2.52530 -2.92537 H -6.55098 3.13717 -3.66881 C 2.22318 -1.21922 3.34825 H 2.24202 -1.59684 4.35841 C -4.82155 1.50940 1.97252 H -4.39002 2.34144 1.42628 C 4.20194 -1.58463 -1.61082 C -5.42570 1.73732 3.20255




S51

H -5.43893 2.74043 3.61619 C 3.27945 -0.64014 2.65262 B 3.55568 0.26721 0.16886 H 4.71655 0.38385 0.40670 C -6.14544 1.05714 -1.01092 H -6.73187 0.52894 -0.26769 C -4.51153 -3.19342 -2.00433 H -4.97892 -3.50172 -2.93401 C 3.45511 -2.36277 -2.48899 H 3.82210 -3.15111 -3.12656 C -6.79097 1.83404 -1.96855 H -7.87409 1.90286 -1.96138 C -3.19769 -3.69478 -0.05530 H -2.62884 -4.39463 0.54803 C 0.84641 -2.41515 -2.96875 H 0.24134 -1.54204 -3.23686 C -0.09736 3.48060 -0.81524 H -0.64757 2.58989 -1.13852 C -0.27761 -1.70049 2.62140 H -0.75723 -1.51865 1.65558 C 1.07794 -3.25733 -4.22576 H 1.64934 -4.16257 -3.99610 H 1.62853 -2.69867 -4.98749 H 0.12488 -3.57206 -4.65932 C 0.05546 -3.19731 -1.90230 H -0.07515 -2.58734 -1.00752 H 0.58916 -4.10798 -1.61208 H -0.93769 -3.47265 -2.26560 C -0.23529 4.55173 -1.90277 H 0.18996 4.21362 -2.85096 H 0.27763 5.47490 -1.61591 H -1.28807 4.79846 -2.06757 C -0.71587 3.94486 0.51431 H -0.21030 4.84129 0.88584 H -0.62920 3.16779 1.27665 H -1.77782 4.17642 0.38750 C -1.04872 -0.90505 3.68436

H -0.61276 -1.04913 4.67772 H -2.09563 -1.22137 3.72592 H -1.03418 0.16357 3.46004 C -0.32400 -3.21050 2.89539 H 0.17503 -3.76787 2.09882 H -1.35937 -3.56044 2.96112 H 0.17000 -3.45730 3.83994 C 5.02669 3.06613 -0.31322 H 5.42915 2.47027 0.51198 C 4.66827 -0.29943 3.12295 H 5.36483 -0.50172 2.30374 C 5.65832 -1.68881 -1.24464 H 6.01243 -0.68958 -0.97457 C 5.83462 -2.59858 -0.01392 H 6.87932 -2.61874 0.31217 H 5.53143 -3.62281 -0.24967 H 5.22069 -2.25802 0.82199 C 6.50730 -2.18657 -2.42120 H 7.56645 -2.20211 -2.14930 H 6.38894 -1.54539 -3.29798 H 6.22868 -3.20419 -2.71001 C 5.39972 4.53173 -0.06152 H 6.48475 4.64062 0.01563 H 4.95358 4.90608 0.86316 H 5.06389 5.17332 -0.88152 C 5.66428 2.55037 -1.61719 H 6.75503 2.62706 -1.57351 H 5.31573 3.13689 -2.47227 H 5.40139 1.50733 -1.80198 C 4.76449 1.20188 3.45466 H 5.78579 1.47268 3.73987 H 4.10022 1.45421 4.28635 H 4.47310 1.81566 2.60024 C 5.08972 -1.15610 4.32221 H 6.12103 -0.93163 4.60707 H 5.02410 -2.22287 4.09464 H 4.45873 -0.95805 5.19374




S52

Absolute energies and corrections

E(B3LYP/6-311

G(d))a ZPEa Hcorra Gcorra D3-corr

NO ‐129.926702 0.004530 0.007835 ‐0.015458 ‐0.000001

MesTpCu-SCPh3 ‐4521.690075 0.969571 1.032134 0.865430 ‐0.192725

MesTpCu-N(O)SCPh3-syn ‐4651.643780 0.977343 1.042723 0.870922 ‐0.188669

MesTpCu-N(O)SCPh3-anti ‐4651.620226 0.977753 1.042980 0.872509 ‐0.194082

MesTpCu-S(CPh3)NO-syn ‐4651.621627 0.976660 1.042619 0.870376 ‐0.200882

MesTpCu-S(CPh3)NO-anti ‐4651.621324 0.976807 1.042846 0.870078 ‐0.200146

MesTpCu-π-complex ‐4651.624265 0.977274 1.042590 0.870372 ‐0.187365

MesTpCu- S(CPh3)/NO ‐4651.627317 0.976719 1.042536 0.870206 ‐0.196328

TS ‐4651.622368 0.975905 1.041315 0.868775 ‐0.193507

iPr2TpCu-SCPh3 ‐4182.293062 0.987869 1.047341 0.888572 ‐0.176078

iPr2TpCu-N(O)SCPh3-syn ‐4312.237366 0.994397 1.056448 0.890633 ‐0.170197

E(B3LYP-D3/6

-311G(d))a ZPEa Hcorra Gcorra

NO ‐129.926703 0.004530 0.007835 ‐0.015458

MesTpCu-SCPh3 ‐4521.902229 0.974709 1.035609 0.880959

MesTpCu-N(O)SCPh3-syn ‐4651.850994 0.981430 1.044800 0.884243

MesTpCu-N(O)SCPh3-anti ‐4651.827600 0.981899 1.044988 0.885372

MesTpCu-S(CPh3)NO-syn ‐4651.836977 0.981023 1.045080 0.882240

MesTpCu-S(CPh3)NO-anti ‐4651.837457 0.981684 1.045268 0.884534

MesTpCu-π-complex ‐4651.831310 0.981630 1.044684 0.885009

MesTpCu- S(CPh3)/NO ‐4651.838125 0.980312 1.044586 0.880097




S53

iPr2TpCu-SCPh3 ‐4182.476608 0.992085 1.050062 0.899146

iPr2TpCu-N(O)SCPh3-syn ‐4312.414182 0.998154 1.058816 0.899976

a Values are given in Hartrees Complete reference for Gaussian 09 (Reference 44 from manuscript) 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. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, 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, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian 09, Revision D.01, Gaussian, Inc., Wallingford CT, 2009.


suementary inrmatin - nature · mestpcu-scph 3 ( 1b ) were made by dissolving crystals in ch 2 cl 2...

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