Homogeneous CO Hydrogenation: Ligand Effects on the Lewis Acid ...

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Crystallographic characterization, which would determine which oxygen was methylated, has been thus far elusive, and the material was not further purified or characterized. Figure S90. 1 H NMR. Figure S91. 31 P{ 1 H} NMR. S82
D. Mechanism Studies on the Reduction of [1-E 2] + . Reaction of [1-E 2][BF 4] with [HPt][PF 6] at -40 °C. A J-Young NMR tube was charged with a ~0.2 mL C 6D 5Cl solution of 22.4 mg (0.0213 mmol) [1-E 2][BF 4]. The solution was frozen in a liquid nitrogen cooled cold well in the glove box. A ~0.1 mL layer of C 6D 5Cl was added, and the tube was cooled to freeze the solvents again. Finally, a layer of ~0.3 mL C 6D 5Cl solution of 13.6 mg (0.0213 mmol) [HPt][PF 6] was added, and the solution frozen. The tube was sealed, removed from the glove box, and inserted into a dry ice / acetone bath to keep the contents of the tube frozen. Meanwhile, the NMR probe was cooled to -40 °C. The tube was allowed to just start to thaw, at which point it was shaken vigorously for a few seconds, and then inserted into the -40 °C probe. NMR spectra were obtained at various times and temperatures, with the temperature slowly being raised to 0 °C, at which point the reaction was complete. In separate experiments a broad 31 P signal at -5.9, slightly downfield of [HPt][PF 6] (δ -7.2) was always observed (sometimes an additional sharp peak for [HPt][PF 6] was observed), appearing to be an intermediate of hydride transfer from Pt to [1-E 2] + . A set of two doublets at δ 1.15 (J PP = 71 Hz) and δ 4.5 (J PP = 75 Hz) were also observed, which disappeared at roughly the same rate as the broad hydride signal. S83
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Homogeneous <stron
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I. General Considerations. All air-
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characteristics that matched the pu
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Figure S3. 1 H NMR timecourse. Reac
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Reaction of [1-Ph 2][BF 4] with [HP
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NMR Scale Reaction of [1-Ph 2][BF 4
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Synthesis of mer,trans-(PPh 3) 2Re(
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III. Synthesis of Complexes with Pe
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Figure S13. 31 P{ 1 H} NMR. Figure
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vessel was sealed and heated to 120
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Figure S18. 13 C{ 1 H} NMR. Figure
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Figure S20. 1 H NMR. Figure S21. 31
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Synthesis of mer,trans-(Ph 2PCHCH 2
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Figure S26. 13 C{ 1 H} NMR. Synthes
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Figure S29. 13 C{ 1 H} NMR. Synthes
Page 31 and 32: Figure S31. 31 P{ 1 H} NMR. Figure
Page 33 and 34: NMR (CD 2Cl 2, 125 MHz): δ 35.88 (
Page 35 and 36: Synthesis of trans-[(Ph 2PCH 2CHCH
Page 37 and 38: Figure S39. 13 C{ 1 H} NMR (with re
Page 41 and 42: Figure S43. 1 H NMR. Figure S44. 31
Page 43 and 44: Synthesis of [(Ph 2P(CH 2) 2B(C 8H
Page 45 and 46: Figure S49. 19 F NMR. Figure S50. 1
Page 47 and 48: = 10.2, 16.4, 2H, Ph 2PCH 2CH 2B(C
Page 49 and 50: Figure S55. 11 B{ 1 H} NMR (broad u
Page 53 and 54: (C 6D 5Cl, 300 MHz): δ 1.08 (br m,
Page 55 and 56: Figure S63. 11 B{ 1 H} NMR (broad u
Page 57 and 58: Figure S64. 1 H NMR. Figure S65. 31
Page 59 and 60: Figure S67. 1 H NMR (formyl region)
Page 61 and 62: environments could be B-O bond brea
Page 63 and 64: Figure S69. 1 H NMR (
Page 65 and 66: Figure S73. 1 H- 1 H gCO</s
Page 67 and 68: Reaction of 2-M 2 with pyridine. A
Page 69 and 70: € B. Pulsed Gradient Spin-Echo Di
Page 71 and 72: epeated. If 2-E 2 were strictly mon
Page 73 and 74: Figure S80. 31 P{ 1 H} NMR. Thermol
Page 75 and 76: Figure S81. 1 H NMR of in-situ gene
Page 77 and 78: Figure S85. 13 C{ 1 H} NMR. Figure
Page 79 and 80: Figure S89. 1 H- 13 C gHMBC. Reacti
Page 81: location as [1-E 2][BF 4]. Thus we
Page 85 and 86: emoved from the cold bath and allow
Page 89 and 90: Figure S98. 1 H NMR (20 °C), hydri
Page 91 and 92: of H 2), with the other P-containin
Page 93 and 94: was apparent. Attempts to isolate a
Page 95 and 96: Figure S105. 13 C{ 1 H} NMR. Figure
Page 97 and 98: Reaction of [1-E 2-Mn][BF 4] with 2
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Page 103 and 104: Figure S116. 1 H NMR. Figure S117.
Page 105 and 106: Figure S119. 31 P{ 1 H} NMR. Reacti
Page 107 and 108: and instead a mixture of 2-M 2, unr
Page 109 and 110: (0.0264 mmol) solid [1-E 2][BF 4],
Page 111 and 112: Figure S124. 31 P{ 1 H} NMR. Reacti
Page 113 and 114: of ~2:1 formyl:hydride, which conve
Page 117 and 118: Decomposition of 2-M 1. While searc
Page 119 and 120: Figure S133. 1 H{ 31 P} NMR. Figure
Page 121 and 122: Reaction of [1-M 1][BAr F 4] with [
Page 125 and 126: Figure S140. 1 H NMR time course. B
Page 127 and 128: the only Re species, but after 2.5
Page 129 and 130: Figure S143. 1 H NMR. Figure S144.
Page 131 and 132: Figure S147. 1 H- 1 H gCO</
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Figure S151. Reaction time course (
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one broad doublet), 188.27 (d, J PC
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Low temperature monitoring of the r
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D. Reductions of trans-[(PPh 3)(Ph
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Figure S159. 1 H NMR (with some res
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Figure S163. 1 H- 1 H gCO</
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Reaction of [Na][(PPh 3)(Ph 2P(CH 2
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Figure S168. 13 C{ 1 H} NMR. E. Red
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Figure S170. 31 P{ 1 H} NMR (initia
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VII. Crystallographic Details. Tabl
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Table 1 (cont.) Structure solution
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S155
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S157
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S159
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S161
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S163
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C(17A) 7415(2) 3268(1) 5199(1) 15(1
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C(20B) 5314(2) 1139(1) 8060(1) 20(1
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Table 3. Selected bond lengths [Å]
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C(38A)-C(39A) 1.381(4) C(39A)-C(40A
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O(4A)-C(4A)-Re(1) 122.6(2) C(6A)-C(
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C(28B)-C(23B)-P(2B) 121.5(2) C(25B)
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Table 5. Anisotropic displacement p
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C(46A) 430(20) 201(18) 420(20) -37(
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C(52C) 620(30) 500(30) 620(30) 30(2
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Completeness to θ = 36.56° 86.5 %
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Refinement of F 2 against ALL refle
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S187
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S189
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S191
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S193
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S195
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B(1) 1715(2) 6994(1) 4782(1) 20(1)
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F(17) 4266(1) 11296(1) 3213(1) 32(1
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C(39A)-C(40A) 1.535(3) C(39A)-C(46A
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C(14)-C(15)-C(16) 119.7(2) C(15)-C(
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F(15)-C(68)-C(67) 115.0(2) C(63)-C(
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C(44B) 1370(60) 630(40) 580(30) 20(
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Table 1. Crystal data and structure
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S217
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S219
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S221
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S223
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S225
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Table 2. Atomic coordinates ( x 10
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F(2) 6539(1) 330(1) 6074(1) 63(1) 1
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Table 4. Bond lengths [Å] and angl
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C(20A)-C(15A)-P(1) 119.8(2) C(17A)-
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O(8) 465(10) 298(8) 275(8) 14(6) 66
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Index ranges -20 ≤ h ≤ 21, -38
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e even larger. All esds (except the
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S243
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S245
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C(34) 6283(2) 5342(1) 3204(1) 36(1)
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C(92) -899(2) 7522(1) 2196(1) 50(1)
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C(75)-C(80) 1.393(3) C(76)-C(77) 1.
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C(71)-B(3)-C(66) 111.6(2) O(10)-B(4
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C(83)-C(82)-C(81) 120.3(3) C(84)-C(
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C(34) 354(19) 227(18) 490(20) -17(1
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C(92) 660(20) 480(20) 303(18) -43(1
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Completeness to θ = 26.41° 98.1 %
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e even larger. All esds (except the
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S273
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S275
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C(39) 8573(8) 10016(6) 2455(7) 27(3
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C(6)-Re(2)-P(2) 94.7(4) C(7)-Re(2)-
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C(33)-C(34) 1.360(17) C(33)-C(38) 1
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C(40)-C(39)-P(2) 121.6(10) C(44)-C(
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C(39) 270(80) 380(70) 170(70) 100(6
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θ range for data collection 1.84 t
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covariance matrix. The cell esds ar
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S295
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S297
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C(31)-C(32) 1.499(7) C(32)-C(33) 1.
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___________________________________
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C(13) 200(30) 200(30) 190(30) -50(2
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θ range for data collection 1.76 t
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covariance matrix. The cell esds ar
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S313
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S315
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C(42) 8268(1) 4361(1) 5254(1) 21(1)
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O(7)-Na(1)-O(6) 99.94(3) O(3)-Na(1)
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___________________________________
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C(13) 117(2) 100(2) 95(2) -17(2) -2
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Table 1. Crystal data and structure
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S333
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S335
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S337
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C(17) 2210(1) 7422(1) 2046(1) 21(1)
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C(38)-C(39) 1.3936(11) C(40)-C(45)
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C(1A)-C(2A)-C(3A) 120.0 C(4A)-C(3A)
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C(4A) 499(16) 390(14) 387(15) -71(1
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