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

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C(42) 247(3) 250(4) 164(3) -84(2) -31(2) -104(3) C(43) 264(3) 199(3) 208(3) -95(3) -32(3) -107(3) C(44) 208(3) 140(3) 177(3) -51(2) -24(2) -80(2) C(45) 160(3) 164(3) 177(2) 8(2) -35(2) -95(2) C(46) 265(3) 198(3) 149(2) 32(2) -24(2) -134(3) C(47) 294(4) 335(4) 158(3) 85(3) -87(3) -188(4) C(48) 193(3) 232(3) 171(3) 32(2) -71(2) -123(3) C(49) 171(3) 163(3) 180(3) -18(2) -49(2) -57(2) C(50) 145(3) 134(3) 246(3) -16(2) -18(2) -65(2) C(51) 274(4) 237(4) 172(3) 37(2) -52(3) -132(3) C(52) 162(3) 190(3) 222(3) 15(2) -74(2) -80(2) C(53) 284(4) 208(3) 177(3) -25(3) -51(3) -2(3) C(54) 322(4) 209(4) 159(3) -21(2) -19(3) -31(3) C(55) 405(5) 192(4) 262(4) -39(3) -65(3) -84(4) C(56) 394(5) 228(4) 256(4) 30(3) -114(3) -110(4) ______________________________________________________________________________ S328
Table 1. Crystal data and structure refinement for 12 (AJMM50) (CCDC 738920). Empirical formula C 45H 48BO 4P 2Re • ½ (C 6H 5Cl) Formula weight 968.06 Crystallization Solvent Chlorobenzene Crystal Habit Block Crystal size 0.27 x 0.22 x 0.19 mm 3 Crystal color Yellow Data Collection Type of diffractometer Bruker KAPPA APEX II Wavelength 0.71073 Å MoKα Data Collection Temperature 100(2) K θ range for 9655 reflections used in lattice determination 2.42 to 53.01° Unit cell dimensions a = 11.4898(4) Å α= 80.831(2)° Volume 2100.11(13) Å 3 Z 2 Crystal system Triclinic Space group P-1 Density (calculated) 1.531 Mg/m 3 F(000) 978 θ range for data collection 1.68 to 53.10° Completeness to θ = 53.10° 94.1 % b = 13.5141(5) Å β= 84.498(2)° c = 15.1385(5) Å γ = 64.883(2)° S329
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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
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Table 1 (cont.) Structure solution
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S217
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S219
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S221
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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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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 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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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
Page 277 and 278: Table 2. Atomic coordinates ( x 10
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 287 and 288: Table 5. Anisotropic displacement p
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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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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Page 319 and 320: C(42) 8268(1) 4361(1) 5254(1) 21(1)
Page 321 and 322: Table 4. Bond lengths [Å] and angl
Page 323 and 324: O(7)-Na(1)-O(6) 99.94(3) O(3)-Na(1)
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Page 327: C(13) 117(2) 100(2) 95(2) -17(2) -2
Page 331 and 332: Table 1 (cont.) Structure solution
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Page 339 and 340: C(17) 2210(1) 7422(1) 2046(1) 21(1)
Page 341 and 342: Table 3. Selected bond lengths [Å]
Page 343 and 344: C(38)-C(39) 1.3936(11) C(40)-C(45)
Page 345 and 346: C(1A)-C(2A)-C(3A) 120.0 C(4A)-C(3A)
Page 347 and 348: Table 5. Anisotropic displacement p
Page 349 and 350: C(4A) 499(16) 390(14) 387(15) -71(1
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