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 29574 / 117 / 983 Treatment of hydrogen atoms Riding Goodness-of-fit on F 2 2.971 Final R indices [I>2σ(I), 24164 reflections] R1 = 0.0371, wR2 = 0.0708 R indices (all data) R1 = 0.0515, wR2 = 0.0713 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 4.938 and -2.452 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. One of the borabicylcononane ligands is disordered by a rotation around the B-C bond. Both the minor (34%) and major (66%) components were restrained to the same geometry as the ordered ligand. The minor component was refined as isotropic and the major component was refined as anisotropic but was restrained to simulate isotropic behavior. The dichloroethane solvent of crystallization was also disordered with both orientations apparently sharing one common Cl site and the ethyl portion flipped about the approximated Cl-Cl vector. The minor component (34%) was refined isotropically and the major component (66%) anisotropically; no geometry restraints were imposed. S184
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 be 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. S185
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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</
Page 133 and 134: Figure S151. Reaction time course (
Page 135 and 136: one broad doublet), 188.27 (d, J PC
Page 137 and 138: Low temperature monitoring of the r
Page 139 and 140: D. Reductions of trans-[(PPh 3)(Ph
Page 141 and 142: Figure S159. 1 H NMR (with some res
Page 143 and 144: Figure S163. 1 H- 1 H gCO</
Page 145 and 146: 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
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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: Completeness to θ = 36.56° 86.5 %
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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)-
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Table 5. Anisotropic displacement p
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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 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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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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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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C(4A) 499(16) 390(14) 387(15) -71(1
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