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

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C(15)-C(16) 1.534(4) C(16)-C(17) 1.548(4) C(17)-C(18) 1.540(4) C(19)-C(20) 1.380(3) C(19)-C(24) 1.404(3) C(20)-C(21) 1.389(3) C(21)-C(22) 1.377(3) C(22)-C(23) 1.371(4) C(23)-C(24) 1.377(3) C(25)-C(30) 1.384(4) C(25)-C(26) 1.394(4) C(26)-C(27) 1.387(4) C(27)-C(28) 1.376(5) C(28)-C(29) 1.386(5) C(29)-C(30) 1.384(4) C(31)-C(36) 1.383(3) C(31)-C(32) 1.393(3) C(32)-C(33) 1.389(3) C(33)-C(34) 1.373(4) C(34)-C(35) 1.367(4) C(35)-C(36) 1.383(3) C(37)-C(42) 1.380(3) C(37)-C(38) 1.400(3) C(38)-C(39) 1.380(3) C(39)-C(40) 1.377(3) C(40)-C(41) 1.387(3) C(41)-C(42) 1.389(3) C(43)-C(44) 1.536(3) C(45)-C(52) 1.533(3) C(45)-C(46) 1.538(3) C(46)-C(47) 1.524(3) C(47)-C(48) 1.523(3) C(48)-C(49) 1.545(3) C(49)-C(50) 1.538(3) C(50)-C(51) 1.537(3) C(51)-C(52) 1.531(4) C(53)-C(54) 1.389(3) C(53)-C(58) 1.396(3) C(54)-C(55) 1.385(3) C(55)-C(56) 1.371(4) C(56)-C(57) 1.381(4) C(57)-C(58) 1.380(3) C(59)-C(60) 1.391(3) C(59)-C(64) 1.393(3) C(60)-C(61) 1.379(3) C(61)-C(62) 1.386(3) C(62)-C(63) 1.375(3) C(63)-C(64) 1.388(3) C(65)-C(66) 1.532(3) C(67)-C(74) 1.535(3) C(67)-C(68) 1.546(3) C(68)-C(69) 1.526(3) C(69)-C(70) 1.532(3) C(70)-C(71) 1.537(3) C(71)-C(72) 1.547(3) C(72)-C(73) 1.539(4) C(73)-C(74) 1.520(3) C(75)-C(76) 1.384(3) S256
C(75)-C(80) 1.393(3) C(76)-C(77) 1.385(3) C(77)-C(78) 1.378(3) C(78)-C(79) 1.357(4) C(79)-C(80) 1.399(3) C(81)-C(86) 1.386(3) C(81)-C(82) 1.398(3) C(82)-C(83) 1.386(4) C(83)-C(84) 1.370(4) C(84)-C(85) 1.372(3) C(85)-C(86) 1.382(3) C(87)-C(88) 1.526(3) C(89)-C(90) 1.530(4) C(89)-C(96) 1.545(4) C(90)-C(91) 1.534(4) C(91)-C(92) 1.550(4) C(92)-C(93) 1.525(4) C(93)-C(94) 1.530(4) C(94)-C(95) 1.546(4) C(95)-C(96) 1.541(4) C(1A)-C(6A) 1.392(6) C(1A)-C(2A) 1.427(5) C(2A)-C(3A) 1.368(4) C(3A)-C(4A) 1.355(4) C(4A)-C(5A) 1.355(4) C(5A)-C(6A) 1.338(5) C(1B)-C(2B) 1.341(5) C(1B)-C(6B) 1.370(5) C(2B)-C(3B) 1.363(5) C(3B)-C(4B) 1.406(5) C(4B)-C(5B) 1.307(5) C(5B)-C(6B) 1.361(5) C(1D)-C(2D) 1.3900 C(1D)-C(6D) 1.3900 C(2D)-C(3D) 1.3900 C(3D)-C(4D) 1.3900 C(4D)-C(5D) 1.3900 C(5D)-C(6D) 1.3900 C(1E)-C(2E) 1.301(14) C(2E)-C(3E) 1.620(16) C(3E)-C(4E) 1.350(11) C(4E)-C(5E) 1.615(13) C(1)-Re(1)-C(4) 95.62(11) C(1)-Re(1)-C(2) 93.09(11) C(4)-Re(1)-C(2) 171.12(11) C(1)-Re(1)-C(3) 179.94(16) C(4)-Re(1)-C(3) 84.43(12) C(2)-Re(1)-C(3) 86.86(11) C(1)-Re(1)-P(1) 89.41(6) C(4)-Re(1)-P(1) 90.19(7) C(2)-Re(1)-P(1) 88.16(7) C(3)-Re(1)-P(1) 90.56(7) C(1)-Re(1)-P(2) 90.47(6) C(4)-Re(1)-P(2) 90.09(7) C(2)-Re(1)-P(2) 91.58(7) C(3)-Re(1)-P(2) 89.56(7) P(1)-Re(1)-P(2) 179.70(2) S257
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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 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
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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
Page 205 and 206: C(14)-C(15)-C(16) 119.7(2) C(15)-C(
Page 207 and 208: F(15)-C(68)-C(67) 115.0(2) C(63)-C(
Page 209 and 210: Table 5. Anisotropic displacement p
Page 211 and 212: C(44B) 1370(60) 630(40) 580(30) 20(
Page 213 and 214: Table 1. Crystal data and structure
Page 215 and 216: Table 1 (cont.) Structure solution
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Page 227 and 228: Table 2. Atomic coordinates ( x 10
Page 229 and 230: F(2) 6539(1) 330(1) 6074(1) 63(1) 1
Page 231 and 232: Table 4. Bond lengths [Å] and angl
Page 233 and 234: C(20A)-C(15A)-P(1) 119.8(2) C(17A)-
Page 237 and 238: O(8) 465(10) 298(8) 275(8) 14(6) 66
Page 239 and 240: Index ranges -20 ≤ h ≤ 21, -38
Page 241 and 242: e even larger. All esds (except the
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Page 249 and 250: C(34) 6283(2) 5342(1) 3204(1) 36(1)
Page 251 and 252: C(92) -899(2) 7522(1) 2196(1) 50(1)
Page 253 and 254: Table 3. Selected bond lengths [Å]
Page 255: Table 4. Bond lengths [Å] and angl
Page 259 and 260: C(71)-B(3)-C(66) 111.6(2) O(10)-B(4
Page 261 and 262: C(83)-C(82)-C(81) 120.3(3) C(84)-C(
Page 265 and 266: C(34) 354(19) 227(18) 490(20) -17(1
Page 267 and 268: C(92) 660(20) 480(20) 303(18) -43(1
Page 269 and 270: Completeness to θ = 26.41° 98.1 %
Page 271 and 272: e even larger. All esds (except the
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Page 279 and 280: C(39) 8573(8) 10016(6) 2455(7) 27(3
Page 281 and 282: C(6)-Re(2)-P(2) 94.7(4) C(7)-Re(2)-
Page 283 and 284: C(33)-C(34) 1.360(17) C(33)-C(38) 1
Page 285 and 286: C(40)-C(39)-P(2) 121.6(10) C(44)-C(
Page 289 and 290: C(39) 270(80) 380(70) 170(70) 100(6
Page 291 and 292: θ range for data collection 1.84 t
Page 293 and 294: covariance matrix. The cell esds ar
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Page 301 and 302: Table 3. Selected bond lengths [Å]
Page 303 and 304: C(31)-C(32) 1.499(7) C(32)-C(33) 1.
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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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Table 2. Atomic coordinates ( x 10
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C(42) 8268(1) 4361(1) 5254(1) 21(1)
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Table 4. Bond lengths [Å] and angl
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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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Table 5. Anisotropic displacement p
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C(4A) 499(16) 390(14) 387(15) -71(1
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