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

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Table 1 (cont.) Structure solution and Refinement Structure solution program SHELXS-97 (Sheldrick, 2008) Primary solution method Direct methods Secondary solution method Difference Fourier map Hydrogen placement Geometric positions Structure refinement program SHELXL-97 (Sheldrick, 2008) Refinement method Full matrix least-squares on F 2 Data / restraints / parameters 27378 / 0 / 1186 Treatment of hydrogen atoms Riding Goodness-of-fit on F 2 2.100 Final R indices [I>2σ(I), 22663 reflections] R1 = 0.0332, wR2 = 0.0504 R indices (all data) R1 = 0.0463, wR2 = 0.0510 Type of weighting scheme used Sigma Weighting scheme used w=1/σ 2 (Fo 2 ) Max shift/error 0.005 Average shift/error 0.000 Largest diff. peak and hole 1.707 and -1.341 e.Å -3 Special Refinement Details Crystals were mounted on a glass fiber using Paratone oil then placed on the diffractometer under a nitrogen stream at 100K. There are three sites containing solvent, two contain benzene only. The third site is a mixture of benzene and pentane. The benzene in this site was restrained to an ideal hexagon and the pentane had no restraints applied. Refinement of F 2 against ALL reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F 2 , conventional R-factors (R) are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > 2σ( F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R-factors based on ALL data will S240
e even larger. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. S241
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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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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 237 and 238: O(8) 465(10) 298(8) 275(8) 14(6) 66
Page 239: Index ranges -20 ≤ h ≤ 21, -38
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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 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
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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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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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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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