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

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<strong>CO</strong>), 209.03 (br t, J PC ~ 9.9 Hz, <strong>CO</strong>), 307.18 (br, Re=C(OCH 3)CH 2O-). IR (C 6H 6): υ <strong>CO</strong>, 1989, 1857 cm -1 . Anal. calcd. for C 45H 48BO 4P 2Re: C, 59.27; H, 5.31. Found: C, 59.54; H, 5.26; N,
Figure S168. 13 C{ 1 H} NMR. E. Reductions of [(Ph 2P(CH 2) 3B(C 8H 14))Re(<strong>CO</strong>) 5][OTf] ([1-P 1][OTf]). Reaction of [1-P 1][OTf] with [HPt][PF 6]. A 10 mL scintillation vial was charged with 24.6 mg (0.0299 mmol) [1-P 1][OTf], which was dissolved in ~0.6 mL C 6D 5Cl. To the stirring solution was added 19.2 mg (0.0299 mmol) [HPt] + as a solid portionwise. After stirring for a couple minutes, the mixture was transferred to a J- Young NMR tube, and monitored by 1 H and 31 P{ 1 H} NMR. After 30 minutes, the ratio of formyl: Re-H was 1.00:0.03. After 1.5 hours, the ratio was 1.00:0.61. After 2.5 hours the ratio was 1.00:28.68. After 5.5 hours, all of the formyl was consumed. During the course of the reaction what appeared to be a Re-alkyl (4.72, d, J PH = 6.6 Hz) was present; the small (~10 %) amount remained constant over the course of the reaction. NMR spectra data for Re-CHO species: 1 H NMR (C 6D 5Cl, 300 MHz): δ 0.89 (br, 2H, Ph 2PCH 2CH 2CH 2B(C 8H 14)), 1.04 (br, 2H, S147
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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
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D. Mechanism Studies on the Reducti
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emoved from the cold bath and allow
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Figure S98. 1 H NMR (20 °C), hydri
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of H 2), with the other P-containin
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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 101 and 102: Figure S114. 31 P{ 1 H} NMR. Figure
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
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
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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 and 134: Figure S151. Reaction time course (
Page 135 and 136: one broad doublet), 188.27 (d, J PC
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: Reaction of [Na][(PPh 3)(Ph 2P(CH 2
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 %
Page 185 and 186: Refinement of F 2 against ALL refle
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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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