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

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Figure S33. 11 B NMR. Synthesis of mer,trans-(Ph 2PCH 2CHCH 2) 2Re(<strong>CO</strong>) 3Br. A 60 mL Teflon-stoppered pressure tube was charged with 741 mg (1.82 mmol) Re(<strong>CO</strong>) 5Br, 825 mg (3.64 mmol, 2 equiv) Ph 2PCH 2CHCH 2, 15 mL toluene, and a stirbar. The tube was sealed, removed from the glovebox, and heated to 120 °C. After 5 days, the reaction was cooled to ambient temperature, degassed to remove liberated <strong>CO</strong>, and brought into a glovebox. All solvents were removed under vacuum, the solids were washed with 25 mL pentane, and collected on a frit. The white powder was dried, giving 1.28 g (1.59 mmol, 88%) pure mer,trans- (Ph 2PCH 2CHCH 2) 2Re(<strong>CO</strong>) 3Br. 1 H NMR (CD 2Cl 2, 300 MHz): δ 3.62 (m, 4H, Ph 2PCH 2CHCH 2), 4.85 (dd, 4 J PH=1.8 Hz, J HH=17.3 Hz, 2H, Ph 2PCH 2CHCH 2), 4.98 (dd, 4 J PH=1.7 Hz, J HH=10.3 Hz, 2H, Ph 2PCH 2CHCH 2), 5.63 (m, 2H, Ph 2PCH 2CHCH 2), 7.40-7.48 (m, 12H, Ph 2PCH 2CHCH 2), 7.56-7.65 (m, 8H, Ph 2PCH 2CHCH 2). 31 P{ 1 H} NMR (CD 2Cl 2, 121 MHz): δ -0.9 (s). 13 C{ 1 H} S32
NMR (CD 2Cl 2, 125 MHz): δ 35.88 (t, 1 J PC = 14.4 Hz, Ph 2PCH 2CHCH 2), 120.53 (t, 3 J PC = 5.4 Hz, Ph 2PCH 2CHCH 2), 128.76 (t, J PC = 4.7 Hz, m-Ph 2PCH 2CHCH 2), 130.58 (t, 2 J PC = 2.6 Hz, Ph 2PCH 2CHCH 2), 130.68 (br t, J PC < 1 Hz, p-Ph 2PCH 2CHCH 2), 133.36 (t, J PC = 5.0 Hz, o- Ph 2PCH 2CHCH 2), 135.21 (t, 1 J PC = 23.3 Hz, ipso-Ph 2PCH 2CHCH 2), 190.38 (t, 2 J PC = 6.7 Hz, <strong>CO</strong> trans to Br), 192.25 (t, 2 J PC = 8.5 Hz, <strong>CO</strong>). IR (CD 2Cl 2): υ <strong>CO</strong>, 2060, 1958, 1899 cm -1 . Anal. Calcd. for C 33H 30BrO 3P 2Re: C, 49.38; H, 3.77. Found: C, 49.32; H, 3.38. Figure S34. 1 H NMR. S33
Page 1 and 2: Homogeneous <stron
Page 3 and 4: I. General Considerations. All air-
Page 5 and 6: characteristics that matched the pu
Page 7 and 8: Figure S3. 1 H NMR timecourse. Reac
Page 9 and 10: Reaction of [1-Ph 2][BF 4] with [HP
Page 11 and 12: NMR Scale Reaction of [1-Ph 2][BF 4
Page 13 and 14: Synthesis of mer,trans-(PPh 3) 2Re(
Page 15 and 16: III. Synthesis of Complexes with Pe
Page 17 and 18: Figure S13. 31 P{ 1 H} NMR. Figure
Page 19 and 20: vessel was sealed and heated to 120
Page 21 and 22: Figure S18. 13 C{ 1 H} NMR. Figure
Page 23 and 24: Figure S20. 1 H NMR. Figure S21. 31
Page 25 and 26: Synthesis of mer,trans-(Ph 2PCHCH 2
Page 27 and 28: Figure S26. 13 C{ 1 H} NMR. Synthes
Page 29 and 30: Figure S29. 13 C{ 1 H} NMR. Synthes
Page 31: Figure S31. 31 P{ 1 H} NMR. Figure
Page 35 and 36: Synthesis of trans-[(Ph 2PCH 2CHCH
Page 37 and 38: Figure S39. 13 C{ 1 H} NMR (with re
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 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 and 82: 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 S95. 31 P{ 1 H} NMR. Figure
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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
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Figure S105. 13 C{ 1 H} NMR. Figure
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Reaction of [1-E 2-Mn][BF 4] with 2
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(br), 20.3, 24.7, 26.4, 28.7 (br),
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Figure S116. 1 H NMR. Figure S117.
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Figure S119. 31 P{ 1 H} NMR. Reacti
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and instead a mixture of 2-M 2, unr
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(0.0264 mmol) solid [1-E 2][BF 4],
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Figure S124. 31 P{ 1 H} NMR. Reacti
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of ~2:1 formyl:hydride, which conve
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Decomposition of 2-M 1. While searc
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Figure S133. 1 H{ 31 P} NMR. Figure
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Reaction of [1-M 1][BAr F 4] with [
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Figure S140. 1 H NMR time course. B
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the only Re species, but after 2.5
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Figure S143. 1 H NMR. Figure S144.
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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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