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

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C. Reductions of [(Ph 2P(CH 2) 2B(C 8H 14))Re(<strong>CO</strong>) 5][OTf] ([1-E 1][OTf]). Reaction of [(Ph 2P(CH 2) 2B(C 8H 14))Re(<strong>CO</strong>) 5][OTf] ([1-E 1][OTf]) with [HPt][PF 6]. To a stirring solution of 27.5 mg (0.034 mmol) [1-E 1][OTf] in ~0.6 mL C 6D 5Cl was added 24.0 mg (0.037 mmol) [HPt(dmpe) 2][PF 6] as a solid in small portions. After stirring for a minute, the reaction mixture was added to a J-Young NMR tube. After 20 minutes, essentially quantitative conversion to a new species was observed, identified as dinuclear bridging alkyl-dioxycarbene 10-E 1. Filtration followed by removal of solvents gave analytically pure white solids. 1 H NMR (600 MHz, C 6D 5Cl): δ 1.04-1.11 (m, 4H, Ph 2PCH 2CH 2B(C 8H 14)), 1.21 (br, 2H, Ph 2PCH 2CH 2B(C 8H 14)), 1.41 (m, 2H, Ph 2PCH 2CH 2B(C 8H 14)), 1.53-1.58 (m, 6H, Ph 2PCH 2CH 2B(C 8H 14)), 1.65 (br, 2H, Ph 2PCH 2CH 2B(C 8H 14)), 1.70-1.77 (m, 6H, Ph 2PCH 2CH 2B(C 8H 14)), 1.90 (m, 4H, Ph 2PCH 2CH 2B(C 8H 14)), 2.11 (m, 6H, Ph 2PCH 2CH 2B(C 8H 14)), 2.54 (m, 2H, Ph 2PCH 2CH 2B(C 8H 14)), 2.73 (m, 2H, Ph 2PCH 2CH 2B(C 8H 14)), 5.05 (d, J PH = 6.9 Hz, 2H, Re-CH 2O-), 7.14-7.20 (m, 8H, Ph 2PCH 2CH 2B(C 8H 14)), 7.24 (m, 4H, Ph 2PCH 2CH 2B(C 8H 14)), 7.45 (m, 8H, Ph 2PCH 2CH 2B(C 8H 14)). 31 P{ 1 H} NMR (C 6D 5Cl, 121 MHz): δ 3.7 (1P), 13.3 (1P). 13 C{ 1 H} NMR (C 6D 5Cl, 125 MHz): 13.95 (br, Ph 2PCH 2CH 2B(C 8H 14)), 20.59 (br, Ph 2PCH 2CH 2B(C 8H 14)), 23.16 (Ph 2PCH 2CH 2B(C 8H 14)), 23.91 (d, J PC = 17.4 Hz, Ph 2PCH 2CH 2B(C 8H 14)), 25.39 (Ph 2PCH 2CH 2B(C 8H 14)), 25.87 (d, J PC = 27.8 Hz, Ph 2PCH 2CH 2B(C 8H 14)), 26.97 (br, Ph 2PCH 2CH 2B(C 8H 14)), 31.34 (br, Ph 2PCH 2CH 2B(C 8H 14)), 32.78 (Ph 2PCH 2CH 2B(C 8H 14)), 33.21 (Ph 2PCH 2CH 2B(C 8H 14)), 49.88 (d, J PC = 6.6 Hz, Re-CH 2O-), 128.69 (d, JPC = 9.6 Hz, Ph), 130.51 (d, J PC = 24.9 Hz), 132.17 (d, J PC = 9.6 Hz), 132.21 (d, J PC = 9.6 Hz), 133.49 (d, J PC = 44.9 Hz), 135.59 (d, J PC = 46.3 Hz), 184.98 (d, J PC = 44.0 Hz, <strong>CO</strong>), 187.23 (d, J PC = 8.4 Hz, <strong>CO</strong>), 187.68 (d, J PC = 6.9 Hz, <strong>CO</strong>), 187.69 (d, J PC = 7.6 Hz, <strong>CO</strong>; overlap with preceding peak leads to S134
one broad doublet), 188.27 (d, J PC = 48.2 Hz, <strong>CO</strong>), 189.94 (d, J PC = 9.4 Hz, <strong>CO</strong>), 209.61 (d, J PC = 10.5 Hz, Re-C(O-BR 3)OCH 2-). IR (C 6D 5Cl): υ <strong>CO</strong>, 2090 (w), 2084 (w), 2013 (s), 1997 (s), 1965 (s), 1939 (s) cm -1 . Anal. Calcd. for C 54H 58B 2O 10P 2Re 2: C, 49.02; H, 4.42. Found: C, 48.74; H, 4.32. Figure S153. 1 H NMR. Figure S154. 31 P{ 1 H} NMR. S135
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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
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NMR (CD 2Cl 2, 125 MHz): δ 35.88 (
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Synthesis of trans-[(Ph 2PCH 2CHCH
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Figure S39. 13 C{ 1 H} NMR (with re
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Synthesis of [(Ph 2P(CH 2) 2B(C 8H
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Figure S49. 19 F NMR. Figure S50. 1
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= 10.2, 16.4, 2H, Ph 2PCH 2CH 2B(C
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Figure S55. 11 B{ 1 H} NMR (broad u
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(C 6D 5Cl, 300 MHz): δ 1.08 (br m,
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Figure S63. 11 B{ 1 H} NMR (broad u
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Figure S67. 1 H NMR (formyl region)
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environments could be B-O bond brea
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Figure S69. 1 H NMR (
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Figure S73. 1 H- 1 H gCO</s
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Reaction of 2-M 2 with pyridine. A
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€ B. Pulsed Gradient Spin-Echo Di
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epeated. If 2-E 2 were strictly mon
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Figure S80. 31 P{ 1 H} NMR. Thermol
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Figure S81. 1 H NMR of in-situ gene
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Figure S85. 13 C{ 1 H} NMR. Figure
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Figure S89. 1 H- 13 C gHMBC. Reacti
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location as [1-E 2][BF 4]. Thus we
Page 83 and 84: D. Mechanism Studies on the Reducti
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Page 87 and 88: Figure S95. 31 P{ 1 H} NMR. Figure
Page 89 and 90: Figure S98. 1 H NMR (20 °C), hydri
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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
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Page 111 and 112: Figure S124. 31 P{ 1 H} NMR. Reacti
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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
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Page 129 and 130: Figure S143. 1 H NMR. Figure S144.
Page 131 and 132: Figure S147. 1 H- 1 H gCO</
Page 133: Figure S151. Reaction time course (
Page 137 and 138: Low temperature monitoring of the r
Page 139 and 140: D. Reductions of trans-[(PPh 3)(Ph
Page 141 and 142: Figure S159. 1 H NMR (with some res
Page 143 and 144: Figure S163. 1 H- 1 H gCO</
Page 145 and 146: Reaction of [Na][(PPh 3)(Ph 2P(CH 2
Page 147 and 148: Figure S168. 13 C{ 1 H} NMR. E. Red
Page 149 and 150: Figure S170. 31 P{ 1 H} NMR (initia
Page 151 and 152: VII. Crystallographic Details. Tabl
Page 153 and 154: Table 1 (cont.) Structure solution
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Page 165 and 166: C(17A) 7415(2) 3268(1) 5199(1) 15(1
Page 167 and 168: C(20B) 5314(2) 1139(1) 8060(1) 20(1
Page 169 and 170: Table 3. Selected bond lengths [Å]
Page 171 and 172: C(38A)-C(39A) 1.381(4) C(39A)-C(40A
Page 173 and 174: O(4A)-C(4A)-Re(1) 122.6(2) C(6A)-C(
Page 175 and 176: C(28B)-C(23B)-P(2B) 121.5(2) C(25B)
Page 177 and 178: Table 5. Anisotropic displacement p
Page 179 and 180: C(46A) 430(20) 201(18) 420(20) -37(
Page 181 and 182: C(52C) 620(30) 500(30) 620(30) 30(2
Page 183 and 184: 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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Table 3. Selected bond lengths [Å]
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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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Table 5. Anisotropic displacement p
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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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Table 1 (cont.) Structure solution
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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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Table 1 (cont.) Structure solution
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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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