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

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Reaction of 2-M 1 with 2-P 1 (Crossover Experiment). To a stirring ~0.6 mL C 6D 5Cl solution of 19.3 mg (0.0240 mmol) [1-M 1][OTf] was added 15.6 mg (0.0240 mmol) [HPt] + partwise as a solid. The solution was transferred to a J-Young NMR tube, and showed ~90% conversion to 2-M 1 by NMR spectroscopy. The side product was the bridging alkyl as discussed in the synthesis of 2-M 1. Meanwhile, 2-P 1 was prepared by addition of 15.6 mg (0.0240 mmol) solid [HPt] + to 20.0 mg (0.024 mmol) [1-P 1][OTf] with stirring. After one minute of stirring, the contents of the tube containing 2-M 1 were poured into the vial containing 2-P 1, and the reaction mixture was filtered into a J-Young NMR tube. After ~20 minutes, a mixture of both Re-CHO species and a bridging alkyl-metalloester species were observed. After 3 hours, no Re-CHO species remained, and the major species (~90%) was identified by 1 H- 31 P gHMBC NMR as 10-M 1P 1, with the minor product being the initially formed impurity containing only 1C ligands. The 2-D NMR shows correlation of the CH 2 group to the 31 P signal at 0.1, which also correlates to two multiplets in the 1 H NMR at 2.46 and 1.56, belonging to the P ligand, and confirming that the CH 2 is bound the same metal as the P ligand. The other 31 P signal of the major species and the impurity overlap at 2.1 (the amount of impurity stayed roughly the same through the reaction). This resonance correlates to Ph protons and a doublet at 1.75, consistent with the other Re of both bimetallic species being ligated by M. As discussed in the text, this assignment allows for the mechanistic pathway of formation of the bridging alkyl to be identified as nucleophilic attack by oxygen. S124
Figure S140. 1 H NMR time course. Bottom spectrum is 2-M 1 before addition of 2-P 1 (poor shimming due to solid Pt 2+ salts formed during reaction). Middle spectrum is ~20 minutes after addition of 2-P 1 (after filtration). Top spectrum is upon completion of the reaction. Figure S141. 1 H NMR time course. Bottom spectrum is 2-M 1 before addition of 2-P 1. Middle spectrum is ~20 minutes after addition of 2-P 1 (after filtration). Top spectrum is upon completion of the reaction. S125
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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
Page 73 and 74: Figure S80. 31 P{ 1 H} NMR. Thermol
Page 75 and 76: Figure S81. 1 H NMR of in-situ gene
Page 77 and 78: Figure S85. 13 C{ 1 H} NMR. Figure
Page 79 and 80: Figure S89. 1 H- 13 C gHMBC. Reacti
Page 81 and 82: location as [1-E 2][BF 4]. Thus we
Page 83 and 84: D. Mechanism Studies on the Reducti
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Page 87 and 88: Figure S95. 31 P{ 1 H} NMR. Figure
Page 89 and 90: Figure S98. 1 H NMR (20 °C), hydri
Page 91 and 92: of H 2), with the other P-containin
Page 93 and 94: was apparent. Attempts to isolate a
Page 95 and 96: Figure S105. 13 C{ 1 H} NMR. Figure
Page 97 and 98: Reaction of [1-E 2-Mn][BF 4] with 2
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Page 103 and 104: Figure S116. 1 H NMR. Figure S117.
Page 105 and 106: Figure S119. 31 P{ 1 H} NMR. Reacti
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Page 111 and 112: Figure S124. 31 P{ 1 H} NMR. Reacti
Page 113 and 114: of ~2:1 formyl:hydride, which conve
Page 117 and 118: Decomposition of 2-M 1. While searc
Page 119 and 120: Figure S133. 1 H{ 31 P} NMR. Figure
Page 121 and 122: Reaction of [1-M 1][BAr F 4] with [
Page 123: Figure S138. 31 P{ 1 H} NMR. Figure
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Page 129 and 130: Figure S143. 1 H NMR. Figure S144.
Page 131 and 132: 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(
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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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Table 3. Selected bond lengths [Å]
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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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S223
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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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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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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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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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