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

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C(17A) 400(40) 340(30) 210(30) 60(20) 20(20) 100(30) C(18A) 370(40) 320(30) 510(40) 180(30) 20(30) 0(30) C(19A) 670(80) 320(50) 510(70) 170(50) -210(60) -110(50) C(20A) 230(30) 150(30) 280(40) -60(30) 50(30) 90(20) C(15B) 140(20) 720(30) 400(20) 300(20) 0(16) -20(20) C(16B) 370(30) 1760(60) 530(30) 730(30) -150(20) -250(30) C(17B) 580(40) 2610(100) 1170(50) 1530(60) -380(40) -490(50) C(18B) 580(40) 2900(120) 2190(90) 2340(90) -430(50) -570(60) C(19B) 290(30) 1420(70) 1450(90) 1120(60) -70(40) -150(40) C(20B) 200(20) 600(40) 800(40) 450(30) -30(20) 10(30) C(21A) 110(20) 110(20) 170(30) 30(20) -15(19) 30(17) C(22A) 190(30) 240(30) 220(30) -70(20) -50(20) 10(20) C(23A) 190(30) 300(40) 410(40) -120(30) 150(30) -40(30) C(24A) 230(30) 410(40) 380(40) -120(30) -30(30) -150(30) C(25A) 230(30) 530(40) 420(40) -190(30) -120(30) -20(30) C(26A) 230(30) 390(30) 250(30) -40(20) -80(20) 0(20) C(21B) 167(17) 360(20) 165(16) -28(17) -68(13) 4(14) C(22B) 181(16) 290(20) 211(16) -51(14) -8(13) -7(14) C(23B) 124(16) 430(30) 350(20) -137(18) 22(15) -39(16) C(24B) 280(20) 840(40) 660(30) -430(30) -70(20) -160(20) C(25B) 290(20) 1450(50) 560(30) -670(30) -46(19) -200(30) C(26B) 186(16) 1260(40) 310(20) -370(20) -5(14) -110(20) C(41) 295(12) 442(14) 383(13) 124(11) 11(10) 40(10) F(1) 470(9) 276(7) 919(13) 88(8) -13(9) -117(7) F(2) 354(9) 505(10) 964(14) 242(9) 5(9) 146(7) F(3) 1000(15) 743(12) 386(9) 290(8) 50(9) 145(11) O(6) 184(7) 315(8) 381(9) -6(7) 32(6) -2(6) O(7) 276(8) 439(10) 557(11) -140(8) -73(8) -108(7) S236
O(8) 465(10) 298(8) 275(8) 14(6) 66(7) 13(7) S(1) 194(2) 221(2) 263(2) 2(2) 9(2) -37(2) ______________________________________________________________________________ S237
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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 %
Page 185 and 186: Refinement of F 2 against ALL refle
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Page 197 and 198: B(1) 1715(2) 6994(1) 4782(1) 20(1)
Page 199 and 200: F(17) 4266(1) 11296(1) 3213(1) 32(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 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 235: Table 5. Anisotropic displacement p
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 and 256: Table 4. Bond lengths [Å] and angl
Page 257 and 258: C(75)-C(80) 1.393(3) C(76)-C(77) 1.
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 263 and 264: Table 5. Anisotropic displacement p
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(
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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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Table 2. Atomic coordinates ( x 10
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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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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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C(4A) 499(16) 390(14) 387(15) -71(1
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