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

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130.29 (dd, J PC = 2.1, 51.8 Hz), 130.32 (m, o-Ph 2PCHCH 2), 131.33 (dd, J PC = 2.2, 46.8 Hz), 132.87 (m, m-Ph 2PCHCH 2), 132.91, 134.12, 211.3 (br, <strong>CO</strong>). IR (CH 2Cl 2): ν <strong>CO</strong> 2003 cm -1 . HRMS (FAB + ): m/z cald for [C 32H 26MnO 4P 2] + : 591.0687. Found: 591.0672, 563.0756 (-<strong>CO</strong>). Figure S27. 1 H NMR. Figure S28. 31 P{ 1 H} NMR. S28
Figure S29. 13 C{ 1 H} NMR. Synthesis of trans-[(Ph 2P(CH 2) 2B(C 8H 14)) 2Mn(<strong>CO</strong>) 4][BF 4] ([1-E 2-Mn][BF 4]). A 20 mL scintillation vial was charged with 641 mg (0.945 mmol) trans- [(Ph 2PCHCH 2) 2Mn(<strong>CO</strong>) 4][BF 4], and 20 mL CH 2Cl 2 was added. If any residual silver salts were present, as black insoluble solids, the solution was filtered. The solution was added to a 100 mL Teflon-stoppered pressure vessel, to which was then added 692 mg (5.67 mmol) 9-BBN and a stirbar. The yellow solution turned dark orange quickly. The reaction vessel was sealed and moved to a 60 ˚C oil bath, where it was heated with stirring for 10 days. At this time the reaction was allowed to cool to room temperature, and the mixture was filtered through celite, giving a bright yellow solution. The filtrate was concentrated to 3 mL, and 15 mL pentane was added, S29
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: Figure S26. 13 C{ 1 H} NMR. Synthes
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 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
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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 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)
Page 347 and 348:
Page 349 and 350:
C(4A) 499(16) 390(14) 387(15) -71(1
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