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

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C(45A) 1432(6) 8581(4) 8935(3) 57(3) 0.343(3) C(46A) 1167(5) 8106(5) 8443(3) 62(4) 0.343(3) B(2B) 1942(2) 8780(1) 7730(1) 33(1) 0.657(3) C(39B) 2744(2) 8403(2) 7893(1) 40(1) 0.657(3) C(40B) 2638(3) 7641(2) 8069(2) 49(2) 0.657(3) C(41B) 1926(3) 7481(3) 8478(3) 78(2) 0.657(3) C(42B) 1118(3) 7809(2) 8301(3) 106(3) 0.657(3) C(43B) 1169(2) 8586(2) 8145(2) 67(2) 0.657(3) C(44B) 1400(3) 9042(3) 8674(2) 86(2) 0.657(3) C(45B) 2319(3) 9066(4) 8871(2) 87(2) 0.657(3) C(46B) 2998(4) 8869(3) 8453(2) 119(3) 0.657(3) B(3) 1787(2) 9973(1) 2479(1) 15(1) 1 F(1) 3560(1) 9472(1) 2231(1) 24(1) 1 F(2) 4116(1) 9041(1) 1195(1) 37(1) 1 F(3) 3114(1) 9010(1) 203(1) 34(1) 1 F(4) 1507(1) 9459(1) 289(1) 30(1) 1 F(5) 930(1) 9927(1) 1332(1) 23(1) 1 F(6) 1818(1) 11156(1) 1547(1) 28(1) 1 F(7) 1180(1) 12389(1) 1707(1) 52(1) 1 F(8) 301(1) 12706(1) 2710(1) 60(1) 1 F(9) 53(1) 11699(1) 3553(1) 38(1) 1 F(10) 712(1) 10455(1) 3413(1) 23(1) 1 F(11) 2398(1) 8626(1) 2828(1) 25(1) 1 F(12) 1543(1) 7470(1) 2988(1) 37(1) 1 F(13) -151(1) 7466(1) 2871(1) 39(1) 1 F(14) -951(1) 8658(1) 2550(1) 34(1) 1 F(15) -109(1) 9815(1) 2374(1) 23(1) 1 F(16) 3208(1) 10879(1) 2361(1) 23(1) 1 S198
F(17) 4266(1) 11296(1) 3213(1) 32(1) 1 F(18) 4083(1) 10859(1) 4366(1) 38(1) 1 F(19) 2839(1) 9957(1) 4632(1) 33(1) 1 F(20) 1838(1) 9474(1) 3793(1) 24(1) 1 C(51) 2216(1) 9753(1) 1837(1) 15(1) 1 C(52) 3014(1) 9500(1) 1766(1) 18(1) 1 C(53) 3326(2) 9261(1) 1227(1) 23(1) 1 C(54) 2824(2) 9256(1) 727(1) 24(1) 1 C(55) 2016(2) 9484(1) 769(1) 21(1) 1 C(56) 1729(1) 9723(1) 1317(1) 18(1) 1 C(57) 1287(1) 10718(1) 2465(1) 16(1) 1 C(58) 1379(2) 11250(1) 2054(1) 22(1) 1 C(59) 1058(2) 11906(1) 2127(1) 33(1) 1 C(60) 615(2) 12066(1) 2631(1) 36(1) 1 C(61) 490(2) 11560(1) 3053(1) 27(1) 1 C(62) 827(1) 10915(1) 2965(1) 19(1) 1 C(63) 1189(1) 9295(1) 2616(1) 16(1) 1 C(64) 1562(2) 8663(1) 2763(1) 19(1) 1 C(65) 1129(2) 8057(1) 2849(1) 26(1) 1 C(66) 282(2) 8050(1) 2787(1) 27(1) 1 C(67) -122(2) 8653(1) 2627(1) 24(1) 1 C(68) 340(1) 9252(1) 2541(1) 19(1) 1 C(69) 2470(1) 10140(1) 3019(1) 15(1) 1 C(70) 3104(1) 10614(1) 2918(1) 18(1) 1 C(71) 3652(2) 10848(1) 3352(1) 22(1) 1 C(72) 3566(2) 10626(1) 3934(1) 25(1) 1 C(73) 2940(2) 10175(1) 4062(1) 22(1) 1 C(74) 2421(1) 9936(1) 3614(1) 18(1) 1 S199
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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
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
Page 155 and 156: S155
Page 157 and 158: S157
Page 159 and 160: S159
Page 161 and 162: S161
Page 163 and 164: S163
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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Page 189 and 190: S189
Page 191 and 192: S191
Page 193 and 194: S193
Page 195 and 196: S195
Page 197: B(1) 1715(2) 6994(1) 4782(1) 20(1)
Page 201 and 202: Table 3. Selected bond lengths [Å]
Page 203 and 204: 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 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
Page 217 and 218: S217
Page 219 and 220: S219
Page 221 and 222: S221
Page 223 and 224: S223
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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
Page 243 and 244: S243
Page 245 and 246: S245
Page 247 and 248: Table 2. Atomic coordinates ( x 10
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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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Table 3. Selected bond lengths [Å]
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Table 4. Bond lengths [Å] and angl
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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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Table 5. Anisotropic displacement p
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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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Table 2. Atomic coordinates ( x 10
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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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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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Page 349 and 350:
C(4A) 499(16) 390(14) 387(15) -71(1
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