SUPPORTING INFORMATION Carbon Sulfur Bond Cleavage and Hydrodesulfurization of Thiophenes by Tungsten Aaron Sattler and Gerard Parkin,* Department of Chemistry, Columbia University, New York, New York 10027, USA. Received xxxx xx, 2010.
2 EXPERIMENTAL SECTION General Considerations All manipulations were performed using a combination of glovebox, high vacuum, and Schlenk techniques under an argon atmosphere unless otherwise specified. 1 Solvents were purified and degassed by standard procedures. 1 H NMR spectra were measured on Bruker 300 DRX, Bruker 300 DPX, Bruker 400 Avance III, Bruker 400 Cyber-enabled Avance III, and Bruker 500 DMX spectrometers. 1 H chemical shifts are reported in ppm relative to SiMe 4 (δ = 0) and were referenced internally with respect to the protio solvent impurity (δ 7.16 for C 6 D 5 H; δ 2.09 for C 6 D 7 H). 2 13 C NMR spectra are reported in ppm relative to SiMe 4 (δ = 0) and were referenced internally with respect to the solvent (δ 128.06 for C 6 D 6 ). 2 31 P chemical shifts are reported in ppm relative to 85% H 3 PO 4 (δ = 0) and were referenced using P(OMe) 3 (δ = 141.0) as an external standard. Coupling constants are given in hertz. W(PMe 3 ) 4 (η 2 CH 2 PMe 2 )H, W(PMe 3 ) 5 H 2 and W(PMe 3 ) 4 H 4 were prepared by the literature methods; 3 W(PMe 3 ) 3 H 6 was obtained via the photochemical reaction of W(PMe 3 ) 4 H 4 with H 2. 4 Thiophene was purchase from Aldrich and dried over molecular sieves prior to use. Benzothiophene and dibenzothiophene were purchased from Aldrich. d 4 -Thiophene was purchased from CDN Isotopes and dried over molecular sieves prior to use. X-ray structure determinations X-ray diffraction data were collected on a Bruker Apex II diffractometer. Crystal data, data collection and refinement parameters are summarized in Table S1. The structures were solved using direct methods and standard difference map techniques, and were refined by full-matrix least-squares procedures on F 2 with SHELXTL (Version 6.10). 5 Computational Details Calculations were carried out using DFT as implemented in the Jaguar 7.5 (release 207) suite of ab initio quantum chemistry programs. 6 Geometry optimizations were
3 performed with the B3LYP density functional 7 using the 6-31G** (C, H, P and S) and LACVP (W) basis sets. 8 The energies of the optimized structures were reevaluated by additional single point calculations on each optimized geometry using cc-pvtz(-f) correlation consistent triple-ζ basis set for C, H, P, and S and LACV3P for W (Table S2). Synthesis of (η 5 C 4 H 5 S)W(PMe 3 ) 2 (η 2 CH 2 PMe 2 ) (1) A solution of W(PMe 3 ) 4 (η 2 CH 2 PMe 2 )H (50 mg, 0.09 mmol) in d 6 -benzene (ca. 0.7 ml) in an NMR tube equipped with a J. Young valve was treated with thiophene (ca. 0.1 ml, 1.2 mmol). The sample was heated at 60 C for 16 hours and monitored by 1 H NMR spectroscopy, thereby demonstrating conversion to (η 5 C 4 H 5 S)W(PMe 3 ) 2 (η 2 CH 2 PMe 2 ) in ca. 20 % yield. The solution was lyophilized giving a dark black solid residue that was extracted into pentane (ca. 2 ml). The extract was placed at 15 C for 1 week, thereby depositing yellow crystals of (η 5 -C 4 H 5 S)W(PMe 3 ) 2 (η 2 -CH 2 PMe 2 ). The mother liquor was decanted and the crystals were washed with cold pentane (ca. 2 1 ml) and dried in vacuo (6 mg, 14% yield). Crystals of (η 5 C 4 H 5 S)W(PMe 3 ) 2 (η 2 CH 2 PMe 2 ) suitable for X-ray diffraction were obtained from pentane at 15 C. 1 H NMR (C 6 D 6 ): 0.23 [br m, 2H of (η 2 -CH 2 PMe 2 )], 0.82 [d, 2 J P-H = 9, 3H of (η 2 -CH 2 PMe 2 )], 1.16 [d, peak under adjacent peak so can not report coupling, 3H of (η 2 -CH 2 PMe 2 )], 1.19 [d, 2 J P-H = 6, 9H of (PMe 3 ) 2 ], 1.32 [d, 2 J P-H = 8, 9H of (PMe 3 ) 2 ], 1.92 [d, 3 J H-H = 6, 1H of SCHCHCHCH 2 ], 2.67 [br, 1H of SCHCHCHCH 2 ], 3.70 [d, 3 J H-H = 8, 1H of SCHCHCHCH 2 ], 5.04 [t, 3 J H-H = 6, 1H of SCHCHCHCH 2 ], 5.74 [d, 3 J H-H = 6, 1H of SCHCHCHCH 2 ] (the assignments are supported by HSQC spectroscopy). 31 P{ 1 H} NMR (C 6 D 6 ): -75.3 [dd, 2 J P-P = 65, 2 J P-P = 6, 1P of W(η 2 -CH 2 PMe 2 )], -29.5 [dd, 2 J P-P = 19, 2 J P-P = 6, 1P of W(PMe 3 ) 2 ], -15.4 [dd, 2 J P-P = 63, 2 J P-P = 19, 1P of W(PMe 3 ) 2 ] (the assignments are supported by 31 P 1 H HMBC spectroscopy). 13 C{ 1 H} NMR (C 6 D 6 ): -15.7 [m, 1C of (η 2 -CH 2 PMe 2 )], 10.1 [d, 1 J P-C = 15, 1C of (η 2 - CH 2 PMe 2 )], 19.2 [d, 1 J P-C = 25, 1C of (η 2 -CH 2 PMe 2 )], 21.5 [d, 1 J P-C = 23, 3C of (PMe 3 ) 2 ], 24.8 [dd, 1 J P-C = 29, 1 J P-C = 7, 3C of (PMe 3 ) 2 ], 49.1 [t, 2 J P-C = 10, 1C of SCHCHCHCH 2 ], 88.1 [s, 1C
4 of SCHCHCHCH 2 ], 88.3 [s, 1C of SCHCHCHCH 2 ], 111.9 [s, 1C of SCHCHCHCH 2 ] (the assignments are supported by HSQC spectroscopy). Molecular Structure of (η 5 C 4 H 5 S)W(PMe 3 ) 2 (η 2 CH 2 PMe 2 ) Reaction of W(PMe 3 ) 4 (η 2 CH 2 PMe 2 )H with d 4 -Thiophene A solution of W(PMe 3 ) 4 (η 2 CH 2 PMe 2 )H (10 mg, 0.02 mmol) in C 6 D 6 (ca. 0.7 ml) in an NMR tube equipped with a J. Young valve was treated with d 4 -thiophene (ca. 20 µl, 0.24 mmol). The sample was heated at 60 C for 21 hours and monitored by 1 H NMR spectroscopy, thereby demonstrating the formation of (η 5 C 4 D 4 HS)W(PMe 3 ) 2 (η 2 CH 2 PMe 2 ), in which the hydrogen ( 1 H) derived from the cyclometallated PMe 3 is incorporated only into the CH group adjacent to sulfur. The sample was lyophilized, dissolved in C 6 H 6 (ca. 0.7 ml) and analyzed by 2 H NMR spectroscopy, thereby providing additional evidence that there was no deuterium ( 2 H) incorporation into the CH group adjacent to sulfur.
5 Synthesis of W(PMe 3 ) 4 (κ 1 -C α -C 4 H 3 S)H 3 (3) A solution of W(PMe 3 ) 5 H 2 (20 mg, 0.04 mmol) in d 6 -benzene (ca. 0.7 ml) in an NMR tube equipped with a J. Young valve was treated with thiophene (ca. 20 µl, 0.25 mmol) and heated at 80 C. The reaction was monitored by 1 H NMR spectroscopy, thereby demonstrating the formation of W(PMe 3 ) 4 (κ 1 -C α -C 4 H 3 S)H 3 after a period of 6 hours. The solution was lyophilized and the solid obtained was extracted into pentane (2 ml) and placed at 15 C, thereby depositing colorless crystals of W(PMe 3 ) 4 (κ 1 -C α -C 4 H 3 S)H 3 suitable for X ray diffraction. The crystals were isolated, washed with cold pentane ( 15 C) and dried in vacuo giving W(PMe 3 ) 4 (κ 1 -C α -C 4 H 3 S)H 3 (15 mg, 74% yield). Anal. calcd. for W(PMe 3 ) 4 (κ 1 -C α -C 4 H 3 S)H 3 : C, 33.5 %, H, 7.4 %. Found: C, 33.0 %, H, 6.9 %. 1 H NMR (C 6 D 6 ): -3.98 [br m, 2H of WH 3 ], -0.56 [br d, 2 J P-H = 74, 1H of WH 3 ], 1.24 [vt, 2 J P-H =6, 18H of W(PMe 3 ) 4 ], 1.53 [d, 2 J P-H = 7, 18H of W(PMe 3 ) 4 ], 7.20 [m, 2H of C 4 H 3 S], 7.59 [d, 3 J H-H = 2, 1 H of C 4 H 3 S]. 31 P{ 1 H} NMR (C 6 D 6 ): -43.4 [br, 1P of W(PMe 3 ) 4 ], -30.8 [t, 2 J P-P = 19, 1 J W-P = 178, 2P of W(PMe 3 ) 4 ], -18.4 [br, 1P of W(PMe 3 ) 4 ]. Molecular Structure of W(PMe 3 ) 4 (κ 1 -C α -C 4 H 3 S)H 3 (the thienyl ligand exhibits a two-fold rotational disorder and only the major configuration is shown)
6 Reaction of W(PMe 3 ) 5 H 2 with d 4 -Thiophene A solution of W(PMe 3 ) 5 H 2 (20 mg, 0.04 mmol) in d 6 -benzene (ca. 0.7 ml) in an NMR tube equipped with a J. Young valve was treated with d 4 -thiophene (ca. 20 µl, 0.25 mmol). The sample was heated at 60 C for 18 hours, and monitored by 1 H NMR spectroscopy, thereby indicating that there was no hydrogen ( 1 H) incorporation into free d 4 -thiophene. Synthesis of W(PMe 3 ) 4 (SBu n )H 3 (2) A solution of W(PMe 3 ) 4 (η 2 CH 2 PMe 2 )H (60 mg, 0.11 mmol) in benzene (5 ml) in an ampoule was treated with thiophene (ca. 0.2 ml, 2.5 mmol). The mixture was treated with H 2 (ca. 1 atm) and heated at 60 C for 1 day. After this period, the sample was lyophilized to give a dark black solid (53 mg) which, on the basis of 1 H NMR spectroscopy consists of W(PMe 3 ) 4 (SBu n )H 3 (85%), W(PMe 3 ) 3 H 6 (5%) and W(PMe 3 ) 4 H 4 (10%). Correspondingly, the yield of W(PMe 3 ) 4 (SBu n )H 3 is 76%. 1 H NMR (C 6 D 6 ): -4.26 [m, 2H of WH 3 ], -0.46 [m, 1H of WH 3 ], 1.01 [t, 3 J H-H = 8, 3H of SCH 2 CH 2 CH 2 CH 3 ], 1.36 [d, 2 J P-H = 7, 9H of W(PMe 3 ) 4 ], 1.52 [d, 2 J P-H = 8, 9H of W(PMe 3 ) 4 ], 1.60 [vt, 2 J P-H = 6, 18H of W(PMe 3 ) 4 ], 1.67 [m, 2H of SCH 2 CH 2 CH 2 CH 3 ], 1.96 [m, 2H of SCH 2 CH 2 CH 2 CH 3 ], 3.01 [t, 3 J H-H = 8, 2H of SCH 2 CH 2 CH 2 CH 3 ]. 31 P{ 1 H} NMR (C 6 D 6 ): -36.7 [dt, 2 J P-P = 28, 2 J P-P = 16, 1P of W(PMe 3 ) 4 ], -33.7 [t, 2 J P-P = 17, 1 J W-P = 182, 2P of W(PMe 3 ) 4 ], -16.6 [dt, 2 J P-P = 28, 2 J P-P = 17, 1P of W(PMe 3 ) 4 ]. 13 C{ 1 H} NMR (C 6 D 6 ): 14.6 [s, 1C of SCH 2 CH 2 CH 2 CH 3 ], 23.2 [s, 1C of SCH 2 CH 2 CH 2 CH 3 ], 24.5 [vt, 1 J P-C = 24, 6C of W(PMe 3 ) 4 ], 25.3 [d, 1 J P-C = 23, 3C of W(PMe 3 ) 4 ], 32.3 [d, 1 J P-C = 30, 3C of W(PMe 3 ) 4 ], 40.2 [s, 1C of SCH 2 CH 2 CH 2 CH 3 ], 44.1 [dd, 3 J P-C = 16, 3 J P-C = 5, 1C of SCH 2 CH 2 CH 2 CH 3 ] (the assignments are supported by HSQC spectroscopy).
7 Reactivity of W(PMe 3 ) 4 (SBu n )H 3 towards Benzoic Acid A solution of W(PMe 3 ) 4 (SBu n )H 3 (10 mg, 0.02 mmol) in d 6 -benzene (ca. 0.7 ml) was added to a sample of benzoic acid (8 mg, 0.07 mmol) in an NMR tube equipped with a J. Young valve. The solution was analyzed by 1 H NMR spectroscopy, thereby demonstrating the immediate liberation of Bu n SH, which was identified by comparison with the 1 H NMR spectrum with that of an authentic sample. Elimination of But-1-ene from W(PMe 3 ) 4 (SBu n )H 3 A solution of W(PMe 3 ) 4 (SBu n )H 3 (5 mg, 0.01 mmol) in d 6 -benzene (ca. 0.7 ml) in an NMR tube equipped with a J. Young valve was heated at 100 C and monitored by 1 H NMR spectroscopy, thereby demonstrating that W(PMe 3 ) 4 (SBu n )H 3 produces, inter alia, but-1-ene over a period of 18 hours. The presence of but-1-ene was confirmed by comparison of the 1 H NMR spectrum with that of an authentic sample. Reaction of W(PMe 3 ) 3 H 6 towards Thiophene: Formation of W(PMe 3 ) 4 (SBu n )H 3 A solution of W(PMe 3 ) 3 H 6 (5 mg, 0.01 mmol) in d 6 -benzene (ca. 0.7 ml) in an NMR tube equipped with a J. Young valve was treated with thiophene (ca. 20 µl, 0.25 mmol). The sample was heated at 80 C for 5 hours and monitored by 1 H NMR spectroscopy, thereby demonstrating the formation of W(PMe 3 ) 4 (SBu n )H 3. Furthermore, 1 H NMR spectroscopy demonstrated the incorporation of deuterium into both the α and β sites of free thiophene. Reaction of W(PMe 3 ) 3 H 6 towards Thiophene in the Presence of PMe 3 A solution of W(PMe 3 ) 3 H 6 (5 mg, 0.01 mmol) in d 6 -benzene (ca. 0.7 ml) in an NMR tube equipped with a J. Young valve was treated with thiophene (ca. 20 µl, 0.25 mmol) and PMe 3 (ca. 0.05 ml). The sample was heated at 80 C monitored by 1 H NMR spectroscopy, thereby demonstrating the formation of W(PMe 3 ) 4 H 4 over a period of 4 hours. W(PMe 3 ) 4 (SBu n )H 3 was not observed under these conditions.
8 Photochemical Reaction of W(PMe 3 ) 4 H 4 with Thiophene: H/D Exchange Between Thiophene and C 6 D 6 A solution of W(PMe 3 ) 4 H 4 (5 mg, 0.01 mmol) in d 6 -benzene (ca. 0.7 ml) in an NMR tube equipped with a J. Young valve was treated with thiophene (ca. 20 µl, 0.25 mmol). The sample was photolyzed (λ max = 350 nm) for 2.5 hours and monitored by 1 H NMR spectroscopy, thereby demonstrating the incorporation of deuterium into both the α and β sites of free thiophene. In addition, W(PMe 3 ) 4 H 4 converted to W(PMe 3 ) 3 H 6 and W(PMe 3 ) 4 (κ 1 -C α -C 4 H 3 S)H 3 (ca. 5:1). Photochemical Reaction of W(PMe 3 ) 4 H 4 with Thiophene in the presence of PMe 3 A solution of W(PMe 3 ) 4 H 4 (10 mg, 0.02 mmol) in d 6 -benzene (ca. 1.4 ml) was treated with thiophene (ca. 40 µl, 0.50 mmol) and divided equally into two NMR tubes equipped with J. Young valves, one of which was treated with PMe 3 (ca. 0.05 ml). Both samples were photolyzed (λ max = 350 nm) for 2.5 hours, and analyzed by 1 H NMR spectroscopy, thereby demonstrating that PMe 3 inhibited the incorporation of deuterium into free thiophene. Reaction of (η 5 -C 4 H 5 S)W(PMe 3 ) 2 (η 2 -CH 2 PMe 2 ) with H 2 : Formation of W(PMe 3 ) 4 (SBu n )H 3 A solution of (η 5 -C 4 H 5 S)W(PMe 3 ) 2 (η 2 -CH 2 PMe 2 ) (5 mg, 0.01 mmol) in d 6 -benzene (ca. 0.7 ml) in an NMR tube equipped with a J. Young valve was treated with H 2 (ca. 1 atm). The sample was then heated at 60 C and monitored by 1 H NMR spectroscopy, thereby demonstrating the formation of W(PMe 3 ) 4 (SBu n )H 3 after ca. 18 hours. Reaction of (η 5 -C 4 H 5 S)W(PMe 3 ) 2 (η 2 -CH 2 PMe 2 ) with H 2 in the presence of PMe 3 A solution of (η 5 -C 4 H 5 S)W(PMe 3 ) 2 (η 2 -CH 2 PMe 2 ) (5 mg, 0.01 mmol) in d 6 -benzene (ca. 0.7 ml) in an NMR tube equipped with a J. Young valve was treated with PMe 3 (ca. 0.05
9 ml) and then was charged with H 2 (ca. 1 atm). The sample was then heated at 80 C for 3 hours, and monitored by 1 H NMR spectroscopy, indicating that the formation of W(PMe 3 ) 4 (SBu n )H 3 is not prevented by PMe 3. Reactivity of (η 5 -C 4 H 5 S)Mo(PMe 3 ) 2 (η 2 -CH 2 PMe 2 ) towards H 2 A solution of (η 5 -C 4 H 5 S)Mo(PMe 3 ) 2 (η 2 -CH 2 PMe 2 ) (5 mg, 0.01 mmol) in d 6 -benzene (ca. 0.7 ml) in an NMR tube equipped with a J. Young valve was treated with H 2 (ca. 1 atm). The sample was monitored by 1 H NMR spectroscopy, which indicated that no hydrogenation occurs after 60 C for 3 hours, 80 C for 3 hours, 100 C for 3 hours, and 120 C for 12 hours. Reaction of (η 5 -C 4 H 5 S)M(PMe 3 ) 2 (η 2 -CH 2 PMe 2 ) [M = W and Mo] with H 2 A mixture of (η 5 -C 4 H 5 S)W(PMe 3 ) 2 (η 2 -CH 2 PMe 2 ) (6 mg, 0.01 mmol) and (η 5 - C 4 H 5 S)Mo(PMe 3 ) 2 (η 2 -CH 2 PMe 2 ) (5 mg, 0.01 mmol) was placed in an NMR tube equipped with a J. Young valve and treated with d 6 -benzene (ca. 0.7 ml) and mesitylene (ca. 1 µl) as an internal integration standard. The sample was charged with H 2 (ca. 1 atm) and heated at 80 C. The reaction was monitored by 1 H NMR spectroscopy, thereby indicating that, under identical conditions, the tungsten complex, (η 5 - C 4 H 5 S)W(PMe 3 ) 2 (η 2 -CH 2 PMe 2 ), converts to W(PMe 3 ) 4 (SBu n )H 3 while the molybdenum compound (η 5 -C 4 H 5 S)Mo(PMe 3 ) 2 (η 2 -CH 2 PMe 2 ) is inert to hydrogenation. Reactivity of W(PMe 3 ) 4 (κ 1 -C α -C 4 H 3 S)H 3 towards PMe 3 A sample of W(PMe 3 ) 4 (κ 1 -C α -C 4 H 3 S)H 3 (10 mg, 0.02 mmol) in an NMR tube equipped with a J. Young valve was treated with PMe 3 (ca. 0.1 ml) and heated at 80 C for 2 hours. After this period, the volatile components were removed in vacuo and the solid obtained was dissolved in d 6 -benzene (ca. 0.7 ml) and analyzed by 1 H NMR spectroscopy, thereby demonstrating that no W(PMe 3 ) 5 H 2 had formed.
10 Reactivity of W(PMe 3 ) 4 (κ 1 -C α -C 4 H 3 S)H 3 towards H 2 A solution of W(PMe 3 ) 4 (κ 1 -C α -C 4 H 3 S)H 3 (5 mg, 0.01 mmol) in d 6 -benzene (ca. 0.7 ml) in an NMR tube equipped with a J. Young valve was treated with H 2 (ca. 1 atm). The sample was heated at 80 C for 3 hours and monitored by 1 H NMR spectroscopy, thereby demonstrating the formation of a mixture of W(PMe 3 ) 4 (SBu n )H 3 (ca. 60%), W(PMe 3 ) 3 H 6 (ca. 40%), and free thiophene. Reactivity of W(PMe 3 ) 4 (κ 1 -C α -C 4 H 3 S)H 3 towards H 2 in the presence of PMe 3 A solution of W(PMe 3 ) 4 (κ 1 -C α -C 4 H 3 S)H 3 (10 mg, 0.02 mmol) in d 6 -benzene (ca. 1.4 ml) was transferred equally to two NMR tubes equipped with J. Young valves, one of which was treated with PMe 3 (ca. 0.05 ml). The samples were charged with H 2 (ca. 1 atm) and heated at 80 C. The reactions were monitored by 1 H NMR spectroscopy, thereby indicating that, in the absence of PMe 3, W(PMe 3 ) 4 (κ 1 -C α -C 4 H 3 S)H 3 converted completely to W(PMe 3 ) 4 (SBu n )H 3 and W(PMe 3 ) 3 H 6, whereas in the presence of PMe 3, the production of W(PMe 3 ) 4 (SBu n )H 3 is inhibited (ca. 30% conversion), and there is no formation of W(PMe 3 ) 3 H 6. Photochemical Reaction of W(PMe 3 ) 4 (κ 1 -C α -C 4 H 3 S)H 3 with H 2 W(PMe 3 ) 4 (κ 1 -C α -C 4 H 3 S)H 3 (5 mg, 0.01 mmol) was added to an NMR tube equipped with a J. Young valve and treated with d 6 -benzene (ca. 0.7 ml). The sample was treated with H 2 (ca. 1 atm) and photolyzed (λ max = 350 nm) for 2.5 hours. The reaction was monitored by 1 H NMR spectroscopy, indicating that W(PMe 3 ) 3 H 6, free thiophene, and W(PMe 3 ) 4 (SBu n )H 3 formed. Synthesis of (κ 1,η 2 CH 2 CHC 6 H 4 S)W(PMe 3 ) 3 (η 2 CH 2 PMe 2 ) (4) W(PMe 3 ) 4 (η 2 CH 2 PMe 2 )H (30 mg, 0.05 mmol) and benzothiophene (10 mg, 0.07 mmol) was added to an NMR tube equipped with a J. Young valve. The sample was heated at 60 C for 3 hrs. After this period, the tube was pumped down in vacuo and the residue was extracted with pentane (2 ml), and filtered into a small vial. The filtrate was
11 allowed to evaporate slowly over a period of 2 days, thereby depositing orange X-ray quality crystals of (κ 1,η 2 CH 2 CHC 6 H 4 S)W(PMe 3 ) 3 (η 2 CH 2 PMe 2 ). The crystals were washed with cold pentane ( 15 C) and dried in vacuo, giving pure (κ 1,η 2 CH 2 CHC 6 H 4 S)W(PMe 3 ) 3 (η 2 CH 2 PMe 2 ) (5 mg, 15 % yield). Mass Spectrum (FAB+): m/z = 622.01 {M + }. 1 H NMR (C 6 D 6 ): 0.60 [very br, 1H of W(η 2 -CH 2 PMe 2 )], 0.94 [d, 2 J P-H = 8, 6H of W(η 2 -CH 2 PMe 2 )], 1.09 [very br, 9H of W(PMe 3 )], 1.30 [d, 2 J P-H = 7, 9H of W(PMe 3 )], 1.33 [br d, 2 J P-H = 4, 9H of W(PMe 3 )], 1.80 [br m, 1H of (κ 1,η 2 -CH 2 CHC 6 H 4 S)], 2.08 [br m, 1H of (κ 1,η 2 -CH 2 CHC 6 H 4 S)], 3.76 [br m, 1H of (κ 1,η 2 -CH 2 CHC 6 H 4 S)], 6.91 [m, 2H of (κ 1,η 2 -CH 2 CHC 6 H 4 S)], 7.40 [d, 3 J H-H = 7, 1H of (κ 1,η 2 -CH 2 CHC 6 H 4 S)], 7.60 [d, 3 J H-H = 7, 1H of (κ 1,η 2 -CH 2 CHC 6 H 4 S)], 1H of W(η 2 -CH 2 PMe 2 ) not observed. 31 P{ 1 H} NMR (C 6 D 6 ): -87.7 [br, 1P of W(η 2 -CH 2 PMe 2 )], -45.6 [br, 1P of W(PMe 3 ) 3 ], -34.5 [br, 1P of W(PMe 3 ) 3 ], -33.8 [br, 1P of W(PMe 3 ) 3 ]. Molecular Structure of (κ 1,η 2 CH 2 CHC 6 H 4 S)W(PMe 3 ) 3 (η 2 CH 2 PMe 2 )
12 Synthesis of (κ 1,η 2 CH 2 CC 6 H 4 S)W(PMe 3 ) 4 (5) A mixture of W(PMe 3 ) 4 (η 2 CH 2 PMe 2 )H (30 mg, 0.05 mmol) and benzothiophene (10 mg, 0.07 mmol) in an NMR tube equipped with a J. Young valve and treated with d 6 - benzene (ca. 0.7 ml). The sample was heated at 60 C for 18 hours and analyzed by 1 H NMR spectroscopy, thereby demonstrating the formation of, inter alia, (κ 1,η 2 CH 2 CC 6 H 4 S)W(PMe 3 ) 4, on the basis based on similarity of the 1 H and 31 P NMR spectra to those of the molybdenum counterpart, (κ 1,η 2 CH 2 CC 6 H 4 S)Mo(PMe 3 ) 4. 9 (κ 1,η 2 CH 2 CHC 6 H 4 S)W(PMe 3 ) 3 (η 2 CH 2 PMe 2 ) was only observed in small quantities under these conditions. Synthesis of (κ 1,η 2 CH 2 CHC 6 H 4 S)W(PMe 3 ) 4 H (6) and W(PMe 3 ) 4 (κ 1 C α CCHSC 6 H 4 )H 3 (7) (a) A mixture of W(PMe 3 ) 5 H 2 (20 mg, 0.04 mmol) and benzothiophene (6 mg, 0.04 mmol) was placed in an NMR tube equipped with a J. Young valve and treated with d 6 - benzene (ca. 0.7 ml). The sample was heated at 80 C for 6 hours and monitored by 1 H NMR spectroscopy, thereby demonstrating the formation of (κ 1,η 2 CH 2 CHC 6 H 4 S)W(PMe 3 ) 4 H and W(PMe 3 ) 4 (κ 1 C α CCHSC 6 H 4 )H 3 (the approximate ratio of products is 9:1). After this period, the solution was lyophilized, extracted into pentane (2 ml), filtered and placed at 15 C, thereby depositing orange crystals suitable for X ray diffraction. The crystals were washed with cold pentane ( 15 C) and dried in vacuo giving (κ 1,η 2 CH 2 CHC 6 H 4 S)W(PMe 3 ) 4 H (6 mg, 27% yield). Mass spectrum (FAB+): m/z = 549.06 {M + + 1 PMe 3 }. 1 H NMR (C 6 D 6 ): 4.05 [ddt, 2 J P-H = 105, 2 J P-H = 76, 2 J P-H = 14, 1H of W H], 0.98 [d, 2 J P-H = 6, 9H of W(PMe 3 ) 4 ], 1.27 [very br, 9H of W(PMe 3 ) 4 ], 1.40 [d, 2 J P-H = 7, 9H of W(PMe 3 ) 4 ], 1.47 [d, 2 J P-H = 5, 9H of W(PMe 3 ) 4 ], 1.47 [1H of (κ 1,η 2 - CH 2 CHC 6 H 4 S); coincident with a PMe 3 signal and located via a 2D COSY experiment], 1.86 [m, 1H of (κ 1,η 2 -CH 2 CHC 6 H 4 S)], 3.02 [m, 1H of (κ 1,η 2 -CH 2 CHC 6 H 4 S)], 6.84 [dt, 4 J H-H = 1, 3 J H-H = 7, 1H of (κ 1,η 2 -CH 2 CHC 6 H 4 S)], 6.90 [dt, 4 J H-H = 1, 3 J H-H = 7, 1H of (κ 1,η 2 - CH 2 CHC 6 H 4 S)], 7.32 [dd, 4 J H-H = 1, 3 J H-H = 7, 1H of (κ 1,η 2 -CH 2 CHC 6 H 4 S)], 7.62 [dd, 4 J H-H =
13 1, 3 J H-H = 7, 1H of (κ 1,η 2 -CH 2 CHC 6 H 4 S)]. 31 P{ 1 H} NMR (C 6 D 6 ): 39.5 [m, 1P of W(PMe 3 ) 4 ], 34.0 [m, 2P of W(PMe 3 ) 4 ], 33.0 [m, 1P of W(PMe 3 ) 4 ]. Molecular Structure of (κ 1,η 2 CH 2 CHC 6 H 4 S)W(PMe 3 ) 4 H (b) A mixture of W(PMe 3 ) 5 H 2 (20 mg, 0.04 mmol) and benzothiophene (6 mg, 0.04 mmol) was placed in an NMR tube equipped with a J. Young valve and treated with PMe 3 (ca. 0.2 ml). The sample was heated at 80 C for 18 hours, after which period the volatile components were removed in vacuo. The residue was dissolved in d 6 -benzene and analyzed by 1 H NMR spectroscopy, thereby demonstrating the formation of a ca. 2:1 mixture of W(PMe 3 ) 4 (κ 1 C α CCHSC 6 H 4 )H 3 and (κ 1,η 2 CH 2 CHC 6 H 4 S)W(PMe 3 ) 4 H, in addition to unreacted W(PMe 3 ) 5 H 2 and benzothiophene (ca. 30%). The solution was lyophilized and the solid obtained was extracted into pentane (1 ml) and placed at 15 C, thereby depositing large orange X-ray quality crystals of (κ 1,η 2 CH 2 CHC 6 H 4 S)W(PMe 3 ) 4 H and several small colorless X-ray quality crystals of W(PMe 3 ) 4 (κ 1 C α CCHSC 6 H 4 )H 3, which were separated by hand and used for X-ray diffraction. 1 H NMR of W(PMe 3 ) 4 (κ 1 C α CCHSC 6 H 4 )H 3 (C 6 D 6 ): -3.97 [m, 2H of WH 3 ], - 0.48 [br d, 2 J P-H = 70, 1H of WH 3 ], 1.22 [vt, 2 J P-H = 6, 18H of W(PMe 3 ) 4 ], 1.53 [under
14 W(PMe 3 ) 5 H 2 signal, 18H of W(PMe 3 ) 4 ], 7.05 [t, 3 J H-H = 7, 1H of (κ 1 C α CCHSC 6 H 4 )], 7.25 [t, 3 J H-H = 7, 1H of (κ 1 C α CCHSC 6 H 4 )], 7.79 [d, 3 J H-H = 8, 1H of (κ 1 C α CCHSC 6 H 4 )], 7.89 [d, 3 J H-H = 7, 1H of (κ 1 C α CCHSC 6 H 4 )], 1H of (κ 1 C α CCHSC 6 H 4 ) not identified (assignments are tentative because the compound was only obtained in significant quantities as a component of a mixture). Molecular Structure of W(PMe 3 ) 4 (κ 1 C α CCHSC 6 H 4 )H 3 (the benzothienyl ligand exhibits a two-fold rotational disorder and only the major configuration is shown) Synthesis of W(PMe 3 ) 4 (SC 6 H 4 Et)H 3 (8) (a) A mixture of W(PMe 3 ) 4 (η 2 CH 2 PMe 2 )H (50 mg, 0.09 mmol) and benzothiophene (12 mg, 0.09 mmol) in an ampoule was treated with benzene (3 ml) and charged with H 2 (ca. 1 atm). The mixture was heated at 80 C for 12 hours. After this period, the solution was lyophilized to give a light green solid (27 mg) which, on the basis of 1 H NMR spectroscopy consists of W(PMe 3 ) 4 (SC 6 H 4 Et)H 3, W(PMe 4 ) 4 H 4 and benzothiophene (ca. 5:4:1 ratio). Correspondingly, the yield of W(PMe 3 ) 4 (SC 6 H 4 Et)H 3 is 31%. Colorless X-ray quality crystals of W(PMe 3 ) 4 (SC 6 H 4 Et)H 3 were obtained from a solution in pentane at -15 C. W(PMe 3 ) 4 (SC 6 H 4 Et)H 3 can also be obtained quantitatively by addition of H 2 to
15 (κ 1,η 2 CH 2 CHC 6 H 4 S)W(PMe 3 ) 3 (η 2 CH 2 PMe 2 ) (vide infra). 1 H NMR (C 6 D 6 ): -4.12 [quintet, 2 J P-H = 41, 2H of WH 3 ], -0.12 [dt, 2 J P-H = 89, 2 J P-H = 22, 1H of WH 3 ], 1.39 [m, 27H of W(PMe 3 ) 4 ], 1.53 [t, 3 J H-H = 8, 3H of SC 6 H 4 Et], 1.55 [d, 3 J P-H = 7, 9H of W(PMe 3 ) 4 ], 3.38 [q, 3 J H-H = 7, 2H of SC 6 H 4 Et], 7.00 [t, 3 J H-H = 8, 1H of SC 6 H 4 Et], 7.23 [m, 2H of SC 6 H 4 Et], 8.66 [d, 3 J H-H = 8, 1H of SC 6 H 4 Et]. 31 P{ 1 H} NMR (C 6 D 6 ): -36.7 [dt, 2 J P-P = 29, 2 J P-P = 15, 1P of W(PMe 3 ) 4 ], -31.1 [t, 2 J P-P = 17, 1 J W-P = 182, 2P of W(PMe 3 ) 4 ], -15.5 [dt, 2 J P-P = 30, 2 J P-P = 18, 1P of W(PMe 3 ) 4 ]. Mass Spectrum (FAB+): m/z = 629.1 {M + + 1}. Molecular Structure of W(PMe 3 ) 4 (SC 6 H 4 Et)H 3 (b) A mixture of W(PMe 3 ) 3 H 6 (5 mg, 0.01 mmol) and benzothiophene (5 mg, 0.04 mmol) was placed in an NMR tube equipped with a J. Young valve and treated with d 6 - benzene (ca. 0.7 ml). The sample was heated at 60 C for 18 hours and monitored by 1 H NMR spectroscopy, thereby indicating the formation of W(PMe 3 ) 4 (SC 6 H 4 Et)H 3. (c) A mixture of W(PMe 3 ) 4 H 4 (10 mg, 0.02 mmol) and benzothiophene (5 mg, 0.04 mmol) was placed in an NMR tube equipped with a J. Young valve and treated with d 6 - benzene (ca. 0.7 ml). The sample was photolyzed (λ max = 350 nm) for 3 hours, and
16 monitored by 1 H NMR spectroscopy, thereby indicating the formation of W(PMe 3 ) 4 (SC 6 H 4 Et)H 3 and (κ 1,η 2 CH 2 CHC 6 H 4 S)W(PMe 3 ) 4 H (in a ratio of ca. 1:1), together with a small quantity of W(PMe 3 ) 3 H 6 (< 10%). The sample was then charged with H 2 (ca. 1 atm), and (κ 1,η 2 CH 2 CHC 6 H 4 S)W(PMe 3 ) 4 H converted to W(PMe 3 ) 4 (SC 6 H 4 Et)H 3 over a period of several hours at room temperature. Reactivity of (κ 1,η 2 CH 2 CHC 6 H 4 S)W(PMe 3 ) 3 (η 2 CH 2 PMe 2 ) and (κ 1,η 2 - CH 2 CC 6 H 4 S)W(PMe 3 ) 4 towards H 2 (a) A solution of (κ 1,η 2 CH 2 CHC 6 H 4 S)W(PMe 3 ) 3 (η 2 CH 2 PMe 2 ) (5 mg, 0.01 mmol) in d 6 - benzene (ca. 0.7 ml) in an NMR tube equipped with a J. Young valve was treated with H 2 (ca. 1 atm). The sample was monitored by 1 H NMR spectroscopy, thereby demonstrating that (κ 1,η 2 CH 2 CHC 6 H 4 S)W(PMe 3 ) 3 (η 2 CH 2 PMe 2 ) converts to W(PMe 3 ) 4 (SC 6 H 4 Et)H 3 over a period of ca. 30 minutes at room temperature. (b) Although (κ 1,η 2 -CH 2 CC 6 H 4 S)W(PMe 3 ) 4 has not been isolated in pure form (vide supra), a sample in d 6 -benzene that contains (κ 1,η 2 -CH 2 CC 6 H 4 S)W(PMe 3 ) 4 was prepared via the reaction of W(PMe 3 ) 4 (η 2 CH 2 PMe 2 )H with benzothiophene, and was treated with H 2 (ca. 1 atm.). The sample was monitored by 1 H NMR spectroscopy, thereby demonstrating that (κ 1,η 2 -CH 2 CC 6 H 4 S)W(PMe 3 ) 4 converts to W(PMe 3 ) 4 (SC 6 H 4 Et)H 3 over a period of ca. 30 minutes at room temperature. Reaction of (κ 1,η 2 -CH 2 CHC 6 H 4 S)W(PMe 3 ) 4 H with H 2 A solution of (κ 1,η 2 -CH 2 CHC 6 H 4 S)W(PMe 3 ) 4 H (5 mg, 0.01 mmol) in d 6 -benzene (ca. 0.7 ml) in an NMR tube equipped with a J. Young valve was treated with H 2 (ca. 1 atm). The sample was monitored by 1 H NMR spectroscopy, thereby demonstrating that (κ 1,η 2 - CH 2 CHC 6 H 4 S)W(PMe 3 ) 4 H converts to W(PMe 3 ) 4 (SC 6 H 4 Et)H 3 over a period of ca. 30 minutes at room temperature.
17 Elimination of Ethylbenzene from W(PMe 3 ) 4 (SC 6 H 4 Et)H 3 A solution of W(PMe 3 ) 4 (SC 6 H 4 Et)H 3 (5 mg, 0.01 mmol) in d 6 -benzene (ca. 0.7 ml) in an NMR tube equipped with a J. Young valve was heated at 100 C and monitored by 1 H NMR spectroscopy, thereby demonstrating that W(PMe 3 ) 4 (SC 6 H 4 Et)H 3 produces, inter alia, ethylbenzene over a period of 20 hours. The presence of ethylbenzene was confirmed by comparison of the 1 H NMR spectrum with that of an authentic sample. Synthesis of [(κ 2 -C 12 H 8 )W(PMe 3 )](µ-s)(µ-ch 2 PMe 2 )(µ-pme 2 )[W(PMe 3 ) 3 ] (9) A mixture of W(PMe 3 ) 4 (η 2 CH 2 PMe 2 )H (50 mg, 0.09 mmol) and dibenzothiophene (15 mg, 0.08 mmol) was placed in an NMR tube equipped with a J. Young valve. The sample was heated at 100 C for 18 hours, after which period the volatile components (of which methane was identified by 1 H NMR spectroscopy) were removed in vacuo. The black solid residue was extracted with pentane (2 ml), filtered and the filtrate was cooled at 15 C for 3 days. Several different amorphous solids were deposited after this period, one of which was a dark green solid. The dark green solid was hand separated (in air) and returned to an argon glove box. The sample was extracted into pentane (1 ml), filtered, and cooled at 15 C for 1 day, thereby depositing dark green X-ray quality crystals of [(κ 2 -C 12 H 8 )W(PMe 3 )](µ-s)(µ-ch 2 PMe 2 )(µ-pme 2 )[W(PMe 3 ) 3 ] (2 mg, 5% yield). Mass spectrum (FAB+): m/z = 992.0 {M + }, 916.0 {M + PMe 3 }, 840.0 {M + 2PMe 3 }. 1 H NMR (C 6 D 6 ): -2.33 [br m, 2 J H-H = 13, 1H of (µ-ch 2 PMe 2 )], -1.52 [br m, 2 J H-H = 13, 1H of (µ-ch 2 PMe 2 )], 0.39 [d, 2 J P-H = 5, 3H of (µ-pme 2 )], 0.50 [d, 2 J P-H = 6, 3H of (µ- PMe 2 )], 0.63 [d, 2 J P-H = 6, 9H of (PMe 3 )], 1.49 [d, 2 J P-H = 6, 9H of (PMe 3 )], 1.49 [3H of (µ- PMe 2 ); coincident with a PMe 3 signal; assignment is based on integration and is tentative], 1.58 [d, 2 J P-H = 6, 9H of (PMe 3 )], 1.66 [d, 2 J P-H = 8, 9H of (PMe 3 )], 1.99 [d, 2 J P-H = 8, 3H of (µ-pme 2 )], 6.11 [d, 3 J H-H = 6, 1H of (κ 2 -C 12 H 8 )], 6.29 [t, 3 J H-H = 7, 1H of (κ 2 -C 12 H 8 )], 7.16 [1H of (κ 2 -C 12 H 8 ); coincident with the C 6 D 5 H signal and located via a 2D COSY experiment], 7.45 [t, 3 J H-H = 7, 1H of (κ 2 -C 12 H 8 )], 7.50 [dt, 4 J H-H = 1, 3 J H-H = 7, 1H of (κ 2 -
18 C 12 H 8 )], 7.56 [d, 3 J H-H = 7, 1H of (κ 2 -C 12 H 8 )], 7.79 [d, 3 J H-H = 8, 1H of (κ 2 -C 12 H 8 )], 8.23 [dd, 4 J H-H = 1, 3 J H-H = 7, 1H of (κ 2 -C 12 H 8 )]. Molecular Structure of [(κ 2 -C 12 H 8 )W(PMe 3 )](µ-s)(µ-ch 2 PMe 2 )(µ-pme 2 )[W(PMe 3 ) 3 ] Elimination of Biphenyl from [(κ 2 -C 12 H 8 )W(PMe 3 )](µ-s)(µ-ch 2 PMe 2 )(µ- PMe 2 )[W(PMe 3 ) 3 ] in the Presence of H 2 A sample of freshly crystallized [(κ 2 -C 12 H 8 )W(PMe 3 )](µ-s)(µ-ch 2 PMe 2 )(µ- PMe 2 )[W(PMe 3 ) 3 ] (5 mg, 0.01 mmol) was treated with d 6 -benzene (ca. 0.7 ml) and placed in an NMR tube equipped with a J. Young valve. The sample was charged with H 2 (ca. 1 atm) and heated at 60 C. The reaction was monitored by 1 H NMR spectroscopy, thereby demonstrating that [(κ 2 -C 12 H 8 )W(PMe 3 )](µ-s)(µ-ch 2 PMe 2 )(µ-pme 2 )[W(PMe 3 ) 3 ] produces biphenyl over a period of 1.5 hours. The presence of biphenyl was confirmed by comparison of the 1 H NMR spectrum with that of an authentic sample. Further confirmation that the sample contained biphenyl was obtained by lyophilizing the sample and analyzing the 1 H NMR spectrum in CDCl 3.
19 Reactivity of W(PMe 3 ) 3 H 6 towards Dibenzothiophene A mixture of W(PMe 3 ) 3 H 6 (5 mg, 0.01 mmol) and dibenzothiophene (5 mg, 0.03 mmol) was placed in an NMR tube equipped with a J. Young valve and treated with d 6 - benzene (ca. 0.7 ml). The sample was heated at 60 C and monitored by 1 H NMR spectroscopy, thereby demonstrating that deuterium was fully incorporated into the 4 and 6 positions of free dibenzothiophene after a period of 2 hours. The sample was then heated at 80 C for 2 more hours, thereby demonstrating that deuterium was fully incorporated into the 2, 3, 7 and 8 positions of dibenzothiophene. The sample was lyophilized, dissolved in C 6 H 6 (ca. 0.7 ml) and analyzed by 2 H NMR spectroscopy, thereby confirming the incorporation of deuterium into the 2, 3, 4, 6, 7 and 8 positions. 10 Photochemical Reaction of W(PMe 3 ) 4 H 4 with Dibenzothiophene A mixture of W(PMe 3 ) 4 H 4 (5 mg, 0.01 mmol) and dibenzothiophene (5 mg, 0.03 mmol) was placed in an NMR tube equipped with a J. Young valve and treated with d 6 - benzene (ca. 0.7 ml). The sample was photolyzed (λ max = 350 nm) for 2.5 hours, and monitored by 1 H NMR spectroscopy, thereby demonstrating that deuterium was incorporated into the 2, 3, 4, 6, 7 and 8 positions of free dibenzothiophene.
20 Table S1. Crystal, intensity collection and refinement data. (η 5 C 4 H 5 S)W(PMe 3 ) 2 (η 2 CH 2 PMe 2 ) W(PMe 3 ) 4 (κ 1 -C α -C 4 H 3 S)H 3 lattice Orthorhombic Orthorhombic formula C 13 H 31 P 3 SW C 16 H 42 P 4 SW formula weight 496.20 574.29 space group Pna2 1 Pccn a/å 21.784(3) 16.282(3) b/å 10.1799(13) 32.499(6) c/å 8.4941(10) 9.1520(16) α/ 90 90 β/ 90 90 γ/ 90 90 V/Å 3 1883.6(4) 4842.9(15) Z 4 8 temperature (K) 125(2) 149(2) radiation (λ, Å) 0.71073 0.71073 ρ (calcd.), g cm -3 1.750 1.575 µ (Mo Kα), mm -1 6.483 5.118 θ max, deg. 32.66 30.51 no. of data collected 31414 74148 no. of data 6622 7388 no. of parameters 185 237 R 1 [I > 2σ(I)] 0.0264 0.0276 wr 2 [I > 2σ(I)] 0.0430 0.0535 R 1 [all data] 0.0391 0.0386 wr 2 [all data] 0.0456 0.0568 GOF 1.001 1.042
Table S1 (cont). Crystal, intensity collection and refinement data. 21 (κ 1,η 2 CH 2 CHC 6 H 4 S)- W(PMe 3 ) 3 (η 2 CH 2 PMe 2 ) (κ 1,η 2 CH 2 CHC 6 H 4 S)- W(PMe 3 ) 4 H lattice Monoclinic Monoclinic formula C 20 H 42 P 4 SW C 20 H 44 P 4 SW formula weight 622.33 624.34 space group P2 1 /c P2 1 /n a/å 14.6865(16) 18.507(2) b/å 19.500(2) 15.220(2) c/å 18.620(2) 19.118(3) α/ 90 90 β/ 105.020(2) 98.724(2) γ/ 90 90 V/Å 3 5150.4(10) 5322.9(12) Z 8 8 temperature (K) 150(2) 150(2) radiation (λ, Å) 0.71073 0.71073 ρ (calcd.), g cm -3 1.605 1.558 µ (Mo Kα), mm -1 4.820 4.664 θ max, deg. 31.00 30.03 no. of data collected 59799 82546 no. of data 16375 15571 no. of parameters 491 500 R 1 [I > 2σ(I)] 0.0420 0.0514 wr 2 [I > 2σ(I)] 0.0994 0.1065 R 1 [all data] 0.0514 0.0786 wr 2 [all data] 0.1050 0.1178 GOF 1.046 1.038
Table S1 (cont). Crystal, intensity collection and refinement data. 22 W(PMe 3 ) 4 (SC 6 H 4 Et)H 3 W(PMe 3 ) 4 (κ 1 C α CCHSC 6 H 4 )H 3 lattice Triclinic Triclinic formula C 20 H 48 P 4 SW C 20 H 44 P 4 SW formula weight 628.37 624.34 space group P-1 P-1 a/å 9.6343(11) 8.9970(13) b/å 12.1821(14) 10.0679(15) c/å 13.5960(15) 15.782(2) α/ 85.772(2) 80.769(2) β/ 72.371(2) 73.792(2) γ/ 68.5870(10) 84.386(2) V/Å 3 1414.6(3) 1352.8(3) Z 2 2 temperature (K) 125(2) 150(2) radiation (λ, Å) 0.71073 0.71073 ρ (calcd.), g cm -3 1.475 1.533 µ (Mo Kα), mm -1 4.387 4.587 θ max, deg. 30.63 30.51 no. of data collected 22975 21808 no. of data 8664 8217 no. of parameters 260 285 R 1 [I > 2σ(I)] 0.0239 0.0434 wr 2 [I > 2σ(I)] 0.0493 0.0685 R 1 [all data] 0.0290 0.0688 wr 2 [all data] 0.0508 0.0750 GOF 1.013 1.022
Table S1 (cont). Crystal, intensity collection and refinement data. 23 [(κ 2 -C 12 H 8 )W(PMe 3 )](µ-s)(µ- CH 2 PMe 2 )(µ-pme 2 )[W(PMe 3 ) 3 ] lattice Monoclinic formula C 29 H 58 P 6 SW 2 formula weight 992.33 space group P2 1 /n a/å 10.2637(11) b/å 21.784(2) c/å 16.7801(18) α/ 90 β/ 94.326(2) γ/ 90 V/Å 3 3741.0(7) Z 4 temperature (K) 150(2) radiation (λ, Å) 0.71073 ρ (calcd.), g cm -3 1.762 µ (Mo Kα), mm -1 6.475 θ max, deg. 31.50 no. of data collected 63207 no. of data 12439 no. of parameters 366 R 1 [I > 2σ(I)] 0.0253 wr 2 [I > 2σ(I)] 0.0517 R 1 [all data] 0.0371 wr 2 [all data] 0.0556 GOF 1.017
24 Table S2. Cartesian Coordinates and Single Point Energies for Geometry Optimized Structures (Energies in parentheses correspond to the basis set used for geometry optimization). W(PH 3 ) 4 (κ 1 -C C 6 H 3 SC 6 H 4 )H 3 α isomer -2302.22889382127 Hartrees (-2301.91559377007 Hartrees) atom x y z W 10.01325061 1.127323967 1.589201173 H 8.907262161 1.859735428 0.470737517 H 10.28130427-0.572322374 1.824223439 H 9.662706653 0.538989005 3.188704775 P 9.265020819 2.921219866 3.109008632 P 10.75798087 0.100788586-0.509352685 P 12.19424993 0.905235482 2.780247645 P 7.803797702 0.156666135 1.4775344 C 12.54443728 5.051042881-0.75824835 C 13.22297512 3.947437498-0.266949203 C 12.52155051 2.893983397 0.34270501 C 11.12090121 2.863193468 0.520158015 H 13.07814155 5.872812729-1.226870449 H 14.30509183 3.888895471-0.354058821 H 13.12253714 2.049554549 0.671408562 S 8.703136186 4.238961922-0.109917857 C 10.47292386 3.988651149-0.046689063 C 11.1462937 5.076121052-0.659487024
25 C 10.24924567 6.11503024-1.142227871 C 8.894106007 5.800229236-0.903580261 C 7.863846744 6.660831536-1.292471433 C 8.195297988 7.854992125-1.926044795 C 9.537462472 8.184581876-2.171440544 C 10.5594694 7.324025665-1.785306291 H 6.825275763 6.40385397-1.103796423 H 7.406471911 8.536551335-2.232715946 H 9.778492001 9.120498671-2.667546223 H 11.59509573 7.587718916-1.980172248 H 10.58392955 0.820294861-1.712327775 H 12.12247965-0.245429982-0.708710696 H 10.21444197-1.134245376-0.94748393 H 12.87202374 2.015946615 3.343666183 H 12.18496878 0.085675564 3.930061396 H 13.34416645 0.323442705 2.177094637 H 7.884381891 3.076244776 3.412480752 H 9.717780059 2.914760353 4.451612463 H 9.53635255 4.278861092 2.827897819 H 7.270488082-0.305888376 0.24687766 H 7.480087139-0.988470339 2.246797701 H 6.67706316 0.938559354 1.850967185 W(PH 3 ) 4 (κ 1 -C C 6 H 3 SC 6 H 4 )H 3 β isomer -2302.22879922925 Hartrees (-2301.91555680190 Hartrees) atom x y z W 10.21689817 5.993826099 4.847157524
26 H 9.441745451 7.100130879 3.745288065 H 9.466331321 4.881094221 5.959473879 H 10.62250143 6.248252484 6.516879211 P 11.70694508 7.932091936 5.056812759 P 8.77694147 4.361212068 3.718128309 P 11.9171581 4.267109135 5.431407503 P 8.316633177 7.179107385 5.776887695 C 12.78355229 5.713284638 2.752984519 C 11.39385023 5.932242482 2.851954275 C 10.73450834 6.175385824 1.613224691 C 11.37603435 6.163120346 0.380799702 H 9.672683868 6.401862307 1.619337 S 15.17185021 5.422040051 1.257970147 C 13.43857318 5.696995145 1.516478485 C 12.75363827 5.912872302 0.30630441 C 14.97220892 5.594298655-0.490853979 C 13.62982749 5.853927639-0.851793084 C 13.31600001 6.015064994-2.210072859 C 14.31820093 5.917817668-3.169613386 C 15.64428298 5.659069132-2.791729556 C 15.98160972 5.49526575-1.449985381 H 12.29051537 6.215035274-2.508991066 H 14.07284387 6.042839517-4.220441587 H 16.41802595 5.585098256-3.550790385 H 17.00818265 5.294991656-1.157954369 H 10.80899208 6.359747128-0.526340221 H 13.3927861 5.572704213 3.642349061 H 8.640266715 4.398271925 2.309989607
27 H 9.012922455 2.965057993 3.830628104 H 7.39196438 4.30226229 4.029760654 H 7.019671564 6.994904621 5.225157973 H 7.94875809 6.990775844 7.131898595 H 8.276585171 8.597665381 5.784724188 H 13.2800627 4.577035442 5.692461923 H 11.69032259 3.539644582 6.620526562 H 12.17447318 3.164817006 4.577914841 H 11.46083955 8.933551786 6.031563603 H 13.08869451 7.76650227 5.34700318 H 11.86545672 8.787082421 3.943969324 W(PH 3 ) 4 (κ 1 -C C 6 H 3 SC 6 H 4 )H 3 γ isomer -2302.22726383300 Hartrees (-2301.91386160316 Hartrees) atom x y z W 9.924180899 1.181891339 1.561370478 H 8.792014013 2.412522221 1.071057073 H 9.86743811-0.523349485 1.207027592 H 9.850252732 0.152583901 2.96006415 P 9.873832018 2.546005712 3.599957142 P 9.974570363 0.726771617-0.845836578 P 12.21852557 0.268292362 1.907008575 P 7.59390201 0.54497894 1.758756863 C 13.13921227 4.537837483 1.129508088 C 12.40816932 3.405048899 1.495055438 C 11.15071185 3.049264603 0.935676641 H 12.84682615 2.792639114 2.279740499
28 C 10.65030209 3.962305206-0.013068774 C 11.3510488 5.111942478-0.409899231 C 12.60870703 5.388910221 0.164191422 S 13.32983745 6.879596612-0.462189531 C 11.9287921 7.147427265-1.508608767 C 10.95597862 6.130366459-1.374797796 C 9.784828866 6.211553293-2.143418641 C 9.601215559 7.279143479-3.015931954 C 10.57867382 8.278227598-3.13577086 C 11.74942653 8.220363757-2.383574964 H 9.023440187 5.44169312-2.053611221 H 8.693524882 7.341059222-3.609493661 H 10.42344523 9.107063427-3.82082061 H 12.50547809 8.994504421-2.475822704 H 14.09592322 4.749088402 1.599856752 H 9.67289115 3.79241844-0.455998374 H 8.924933673 2.288362176 4.62338958 H 11.00677143 2.624361547 4.455718724 H 9.650040775 3.935503174 3.481879035 H 6.765703395 0.484505653 0.605417921 H 7.242721347-0.723788311 2.281915687 H 6.695598718 1.309053168 2.548537818 H 10.00696267 1.806152319-1.76033437 H 11.02554133-0.027155046-1.434134179 H 8.915149313 0.004714843-1.457451742 H 13.04291764 0.638768911 3.005093367 H 12.3121536-1.126996449 2.103841691 H 13.22610019 0.389152438 0.916600311
29 W(PH 3 ) 4 (κ 1 -C C 6 H 3 SC 6 H 4 )H 3 δ isomer -2302.20994399558 Hartrees (-2301.89609370097 Hartrees) atom x y z W 10.09265223 6.176601688 4.744554326 H 9.257661851 6.452004673 3.235333293 H 9.680100301 5.052582196 5.983546148 H 9.797760669 6.86263778 6.324570505 P 10.3455672 8.626213714 4.793874144 P 9.676677267 3.942071485 3.783292427 P 12.1607706 6.132520643 6.171043716 P 7.686737058 6.428743639 4.971867647 C 11.72261227 6.160085596 3.058139276 C 13.53789673 6.625380626 0.834224325 C 11.5241075 7.138199474 2.059188933 C 12.38908577 7.384031756 0.987375903 C 12.87754461 5.326064948 2.851197958 C 13.75141951 5.606484188 1.757588704 S 15.13780167 4.523706582 1.632794788 C 14.5724615 3.60552073 3.014428698 C 13.37184477 4.125455662 3.566420481 C 12.8448026 3.411991435 4.66233208 C 13.47519493 2.277935959 5.167598853 C 14.66458763 1.804279488 4.602091491 C 15.21788173 2.473051207 3.516144797 H 11.93016343 3.750684265 5.128041655 H 13.03399941 1.758738326 6.014044882
30 H 15.15226796 0.920500243 5.003121377 H 16.1367507 2.121015174 3.056068542 H 10.62920711 7.74849308 2.099226992 H 12.15290721 8.169096411 0.272697642 H 14.23291476 6.795333938 0.017377189 H 9.197164686 9.43255609 5.019026897 H 11.15691737 9.243358741 5.784942948 H 10.84658725 9.34181094 3.679977802 H 12.40119665 7.320449257 6.913519814 H 12.31576933 5.241467293 7.261053662 H 13.45553529 6.004127538 5.626997857 H 6.815517868 5.586018621 4.23184245 H 7.058941662 6.270023792 6.231343638 H 7.06227656 7.655397887 4.620105631 H 10.2624724 3.595176978 2.545221394 H 9.909362294 2.718647222 4.458351036 H 8.329013023 3.658997551 3.426991725
31 REFERENCES (1) (a) McNally, J. P.; Leong, V. S.; Cooper, N. J. in Experimental Organometallic Chemistry, Wayda, A. L.; Darensbourg, M. Y., Eds.; American Chemical Society: Washington, DC, 1987; Chapter 2, pp 6-23. (b) Burger, B.J.; Bercaw, J. E. in Experimental Organometallic Chemistry; Wayda, A. L.; Darensbourg, M. Y., Eds.; American Chemical Society: Washington, DC, 1987; Chapter 4, pp 79-98. (c) Shriver, D. F.; Drezdzon, M. A.; The Manipulation of Air-Sensitive Compounds, 2 nd Edition; Wiley-Interscience: New York, 1986. (2) Gottlieb, H. E.; Kotlyar, V.; Nudelman, A. J. Org. Chem. 1997, 62, 7512-7515. (3) Green, M. L. H.; Parkin, G.; Chen, M.; Prout, K. J. Chem. Soc., Dalton Trans. 1986, 2227 2236. (4) Parkin, G. Rev. Inorg.Chem. 1985, 7, 251-297. (5) (a) Sheldrick, G. M. SHELXTL, An Integrated System for Solving, Refining and Displaying Crystal Structures from Diffraction Data; University of Göttingen, Göttingen, Federal Republic of Germany, 1981. (b) Sheldrick, G. M. Acta Cryst. 2008, A64, 112-122. (6) Jaguar 7.5, Schrödinger, LLC, New York, NY 2008. (7) (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652. (b) Becke, A. D. Phys. Rev. A 1988, 38, 3098-3100. (c) Lee, C. T.; Yang, W. T.; Parr, R. G. Phys. Rev. B 1988, 37, 785-789. (d) Vosko, S. H.; Wilk, L.; Nusair, M. Can. J. Phys. 1980, 58, 1200-1211. (e) Slater, J. C. Quantum Theory of Molecules and Solids, Vol. 4: The Self-Consistent Field for Molecules and Solids; McGraw-Hill: New York, 1974. (8) (a) Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 270-283. (b) Wadt, W. R.; Hay, P. J. J. Chem. Phys. 1985, 82, 284-298. (c) Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299-310.
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