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

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S298
Table 2. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for [Na(THF) 3][3-M 1] (AJMM64) (CCDC 781654). U(eq) is defined as the trace of the orthogonalized U ij tensor. ________________________________________________________________________________ x y z U eq ________________________________________________________________________________ Re(1) 2791(1) 3559(1) 2115(1) 16(1) P(1) 3896(1) 4127(1) 1068(1) 14(1) Na(1) 6474(2) 2740(1) 4390(1) 28(1) O(1) 1769(3) 2847(1) 3710(3) 39(1) O(2) 2932(3) 2714(1) 519(3) 32(1) O(3) 356(3) 3808(1) 909(3) 31(1) O(4) 3087(2) 4161(1) 3308(2) 16(1) O(5) 5107(3) 3232(1) 3579(3) 29(1) O(6) 7883(3) 3244(1) 3973(3) 35(1) O(7) 5498(3) 2672(1) 5948(3) 39(1) O(8) 6166(3) 2145(1) 3094(3) 66(1) B(1) 3159(4) 4696(2) 2878(4) 15(1) C(1) 2111(4) 3126(2) 3114(4) 28(1) C(2) 2868(4) 3046(2) 1151(4) 25(1) C(3) 1287(4) 3731(1) 1342(4) 21(1) C(4) 4114(4) 3962(2) 3914(3) 22(1) C(5) 4310(3) 3501(2) 3262(3) 19(1) C(6) 3635(4) 5059(1) 3874(3) 16(1) C(7) 2884(4) 5004(2) 4840(3) 20(1) C(8) 1586(4) 5083(2) 4518(3) 23(1) C(9) 1113(3) 4826(2) 3438(3) 18(1) C(10) 1866(3) 4871(1) 2473(3) 14(1) C(11) 1898(4) 5386(1) 1999(3) 19(1) C(12) 2526(3) 5761(1) 2784(3) 20(1) S299
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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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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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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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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
Page 247 and 248: Table 2. Atomic coordinates ( x 10
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 263 and 264: Table 5. Anisotropic displacement p
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
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 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)
Page 325 and 326: ___________________________________
Page 327 and 328: C(13) 117(2) 100(2) 95(2) -17(2) -2
Page 329 and 330: Table 1. Crystal data and structure
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 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)
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C(4A) 499(16) 390(14) 387(15) -71(1
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