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

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C(63) 246(15) 277(17) 233(15) 6(13) 84(12) -8(13) C(64) 150(14) 198(16) 270(15) -43(12) 46(12) -16(12) C(65) 158(13) 224(16) 184(13) -1(12) 53(11) 18(12) C(66) 184(14) 179(15) 170(13) -9(11) 38(11) 10(12) C(67) 218(14) 196(16) 187(13) 0(11) 18(11) 8(12) C(68) 201(15) 337(19) 204(14) -75(13) -7(11) -30(13) C(69) 238(16) 341(19) 272(15) -38(14) -37(12) 89(14) C(70) 291(17) 244(17) 341(16) 14(14) -62(13) 50(14) C(71) 211(15) 239(17) 260(15) 18(13) -28(12) -27(12) C(72) 297(17) 440(20) 279(16) 173(15) 39(13) 26(15) C(73) 319(17) 490(20) 202(15) 21(15) 45(13) 74(15) C(74) 228(15) 330(18) 222(14) -43(13) -3(12) 14(13) C(75) 112(13) 274(17) 212(14) -56(12) 14(11) -33(12) C(76) 207(15) 248(18) 367(17) -7(14) 79(13) -17(13) C(77) 222(16) 267(18) 466(19) -72(15) 66(14) 10(13) C(78) 203(16) 360(20) 406(18) -152(15) 111(14) -33(14) C(79) 281(16) 340(20) 289(16) -86(14) 123(13) -84(14) C(80) 229(15) 234(17) 278(15) -47(13) 34(12) -52(13) C(81) 210(14) 201(16) 224(14) -7(12) 23(12) -30(12) C(82) 216(16) 570(20) 250(15) -1(15) 23(13) -19(15) C(83) 370(20) 870(30) 219(16) 36(18) 71(15) -67(19) C(84) 383(19) 670(30) 219(16) 22(16) -31(14) -95(18) C(85) 254(16) 430(20) 336(17) 16(15) -63(13) -51(15) C(86) 196(15) 299(18) 277(15) 7(13) 34(12) -37(13) C(87) 209(14) 250(16) 214(14) -17(12) 19(11) -21(12) C(88) 208(15) 268(17) 244(14) -11(13) 9(12) 45(13) C(89) 328(17) 272(18) 370(17) -66(14) 36(14) 25(14) C(90) 620(20) 470(20) 388(19) -129(17) 189(18) 119(19) C(91) 940(30) 540(20) 298(19) -102(18) 190(20) 30(20) S266
C(92) 660(20) 480(20) 303(18) -43(17) -131(16) 106(19) C(93) 348(18) 334(19) 300(16) -107(14) -44(14) 99(15) C(94) 318(18) 500(20) 427(19) -172(17) -166(14) 49(17) C(95) 600(20) 350(20) 490(20) -160(17) -152(17) -34(18) C(96) 397(19) 320(20) 475(19) -135(16) 23(16) 43(16) C(1A) 1470(50) 360(30) 700(30) 140(20) 620(30) 480(30) C(2A) 890(30) 440(30) 760(30) -250(20) 270(30) 10(20) C(3A) 510(20) 580(30) 320(18) -141(18) 39(17) 116(19) C(4A) 420(20) 730(30) 365(19) -107(19) 98(17) 130(20) C(5A) 440(20) 1120(40) 400(20) -180(20) -42(19) 280(20) C(6A) 990(40) 960(40) 310(20) -80(20) 20(20) 710(30) C(1B) 1910(60) 860(40) 620(30) 70(30) 270(40) -370(40) C(2B) 1830(60) 700(40) 1010(40) -30(30) 240(40) -680(40) C(3B) 820(30) 670(30) 1080(40) -190(30) 220(30) -250(30) C(4B) 730(30) 610(30) 830(30) -10(30) 340(30) 50(20) C(5B) 820(30) 540(30) 690(30) -120(20) 30(20) 140(20) C(6B) 980(40) 660(30) 730(30) -30(30) 100(30) -150(30) ______________________________________________________________________________ S267
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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
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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
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 and 236: Table 5. Anisotropic displacement p
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 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 265: C(34) 354(19) 227(18) 490(20) -17(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 275 and 276: S275
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.
Page 305 and 306: ___________________________________
Page 307 and 308: C(13) 200(30) 200(30) 190(30) -50(2
Page 309 and 310: θ range for data collection 1.76 t
Page 311 and 312: covariance matrix. The cell esds ar
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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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