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

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X-ray Crystallography Procedures. X-ray quality crystals were grown as indicated in the experimental procedures for each complex. The crystals were mounted on a glass fiber with Paratone-N oil. Structures were determined using direct methods with standard Fourier techniques using the Bruker AXS software package. In some cases, Patterson maps were used in place of the direct methods procedure. Full crystallographic details are provided in the section below. II. Reductions of trans-[(PPh 3) 2Re(<strong>CO</strong>) 4] + ([1-Ph 2] + ). Synthesis of [HPt(dmpe) 2][PF 6] ([HPt][PF 6]). While the published literature procedure is serviceable, 10 certain alterations improved the yield in our hands. In particular, the reaction was run more dilute to ensure that all [HPt] + remained in solution, and the use of EtOH (which appeared to decompose [HPt] + at a reasonably quickly) was avoided. A 500 mL round bottom flask was charged with 1.96 g (2.49 mmol) [Pt(dmpe) 2][PF 6] 2, 200 mL acetonitrile, and a stir bar. With the acetonitrile solution stirring, 0.189 g (4.99 mmol, 2 equiv) NaBH 4 (as a 10 wt% mixture in basic alumina) was added as a solid. The mixture was stirred for ~12 hours, filtered through a fine frit, and the filtrate was dried under vacuum to afford an off-white powder. The crude material contained only [HPt][PF 6] and excess NaBH 4. The desired [HPt][PF 6] was extracted with 15 mL C 6H 5Cl, and filtered away from the insoluble white NaBH 4. The solvent was removed from the filtrate under vacuum, and the very pale yellow solids were washed with 3 x 5 mL Et 2O to afford 1.414 g (88% yield) spectroscopically pure [HPt][PF 6]. This procedure provided material with spectroscopic S4
characteristics that matched the published values well, and also matched samples of [HPt][PF 6] prepared using the literature procedure. Reaction of [HPt][PF 6] with CD 2Cl 2. A J-Young NMR tube was charged with 16 mg (0.0234 mmol) [HPt][PF 6] and ~0.5 mL CD 2Cl 2. The tube was sealed and monitored by 1 H and 31 P{ 1 H} NMR spectroscopy over 1 week. Colorless crystals of [Pt]Cl 2 formed in the tube over the course of the week, and spectroscopic analysis revealed steady disappearance of the hydride resonances of [HPt] + (-11.62, p, J PH = 29.4 Hz, J PtH = 705 Hz) with concomitant growth of a peak at 2.98 (pent, J HD = 1.6 Hz) assigned to CHD 2Cl. Figure S1. 1 H NMR time course (bottom, 1 h; middle, 12 h; top, 1 week): S5
Page 1 and 2: Homogeneous <stron
Page 3: I. General Considerations. All air-
Page 7 and 8: Figure S3. 1 H NMR timecourse. Reac
Page 9 and 10: Reaction of [1-Ph 2][BF 4] with [HP
Page 11 and 12: NMR Scale Reaction of [1-Ph 2][BF 4
Page 13 and 14: Synthesis of mer,trans-(PPh 3) 2Re(
Page 15 and 16: III. Synthesis of Complexes with Pe
Page 17 and 18: Figure S13. 31 P{ 1 H} NMR. Figure
Page 19 and 20: vessel was sealed and heated to 120
Page 21 and 22: Figure S18. 13 C{ 1 H} NMR. Figure
Page 23 and 24: Figure S20. 1 H NMR. Figure S21. 31
Page 25 and 26: Synthesis of mer,trans-(Ph 2PCHCH 2
Page 27 and 28: Figure S26. 13 C{ 1 H} NMR. Synthes
Page 29 and 30: Figure S29. 13 C{ 1 H} NMR. Synthes
Page 33 and 34: NMR (CD 2Cl 2, 125 MHz): δ 35.88 (
Page 35 and 36: Synthesis of trans-[(Ph 2PCH 2CHCH
Page 37 and 38: Figure S39. 13 C{ 1 H} NMR (with re
Page 41 and 42: Figure S43. 1 H NMR. Figure S44. 31
Page 43 and 44: Synthesis of [(Ph 2P(CH 2) 2B(C 8H
Page 45 and 46: Figure S49. 19 F NMR. Figure S50. 1
Page 47 and 48: = 10.2, 16.4, 2H, Ph 2PCH 2CH 2B(C
Page 49 and 50: Figure S55. 11 B{ 1 H} NMR (broad u
Page 53 and 54: (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 S64. 1 H NMR. Figure S65. 31
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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 S85. 13 C{ 1 H} NMR. Figure
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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 S95. 31 P{ 1 H} NMR. Figure
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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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Figure S105. 13 C{ 1 H} NMR. Figure
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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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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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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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Homogeneous CO Hydrogenation: Ligand Effects on the Lewis Acid ...

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