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

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Table 5. Anisotropic displacement parameters (Å 2 x 10 4 ) for [Na(THF) 3][3-E 1Ph 1] (AJMM48) (CCDC 770346). The anisotropic displacement factor exp<strong>on</strong>ent takes <strong>the</strong> form: -2π 2 [ h 2 a* 2 U 11 + ... + 2 h k a* b* U 12 ] ______________________________________________________________________________ U 11 U 22 U 33 U 23 U 13 U 12 ______________________________________________________________________________ Re(1) 61(1) 68(1) 69(1) -10(1) -2(1) -28(1) P(1) 79(1) 80(1) 79(1) -15(1) -2(1) -32(1) P(2) 88(1) 81(1) 103(1) -22(1) 0(1) -34(1) Na(1) 117(1) 148(1) 134(1) 27(1) -28(1) -70(1) O(1) 108(2) 229(3) 202(2) 19(2) -22(2) -95(2) O(2) 225(2) 172(2) 114(2) 34(2) -31(2) -67(2) O(3) 97(2) 173(2) 136(2) 6(2) 3(1) -77(2) O(4) 76(2) 107(2) 95(2) 5(1) -10(1) -45(1) O(5) 206(2) 239(3) 152(2) 74(2) -73(2) -154(2) O(6) 193(2) 151(2) 237(2) 46(2) -85(2) -92(2) O(7) 213(2) 226(3) 145(2) -18(2) -22(2) -92(2) B(1) 90(2) 101(2) 88(2) 4(2) -14(2) -40(2) C(1) 98(2) 107(2) 108(2) -3(2) -19(2) -42(2) C(2) 114(2) 103(2) 102(2) -11(2) -5(2) -42(2) C(3) 88(2) 101(2) 104(2) -11(2) -4(2) -44(2) C(4) 90(2) 146(2) 115(2) 15(2) -19(2) -62(2) C(5) 98(2) 121(2) 95(2) 4(2) -15(2) -51(2) C(6) 106(2) 166(3) 129(2) -30(2) 3(2) -54(2) C(7) 156(3) 222(3) 113(2) -38(2) -2(2) -92(2) C(8) 140(2) 177(3) 113(2) -4(2) -33(2) -79(2) C(9) 99(2) 131(2) 105(2) 15(2) -25(2) -49(2) C(10) 141(2) 144(3) 144(2) 38(2) -53(2) -53(2) C(11) 173(3) 162(3) 159(2) 57(2) -51(2) -95(2) C(12) 137(2) 151(3) 149(2) 24(2) -33(2) -87(2) S326
C(13) 117(2) 100(2) 95(2) -17(2) -21(2) -39(2) C(14) 172(3) 169(3) 162(2) 28(2) -69(2) -103(2) C(15) 221(3) 217(3) 243(3) 16(3) -120(3) -123(3) C(16) 227(3) 229(3) 187(3) -38(2) -109(2) -64(3) C(17) 196(3) 253(4) 109(2) -14(2) -43(2) -48(3) C(18) 150(2) 186(3) 99(2) -1(2) -12(2) -56(2) C(19) 99(2) 110(2) 107(2) -25(2) 7(2) -37(2) C(20) 141(2) 121(2) 193(3) -40(2) 40(2) -37(2) C(21) 162(3) 154(3) 247(3) -68(2) 65(2) -25(2) C(22) 145(3) 213(3) 191(3) -71(2) 57(2) -55(2) C(23) 151(3) 196(3) 159(2) -43(2) 49(2) -86(2) C(24) 133(2) 134(2) 132(2) -30(2) 22(2) -60(2) C(25) 127(2) 100(2) 101(2) -5(2) -15(2) -56(2) C(26) 112(2) 107(2) 109(2) -8(2) -20(2) -23(2) C(27) 137(2) 101(2) 133(2) -20(2) 6(2) -59(2) C(28) 158(3) 136(3) 354(4) 9(3) 56(3) -61(2) C(29) 219(4) 196(4) 394(5) -16(3) 101(3) -120(3) C(30) 294(4) 175(3) 177(3) -21(2) 41(3) -153(3) C(31) 269(4) 126(3) 227(3) 25(2) -4(3) -90(3) C(32) 176(3) 117(3) 223(3) 13(2) 6(2) -51(2) C(33) 101(2) 94(2) 169(2) -32(2) 2(2) -33(2) C(34) 123(2) 148(3) 215(3) -62(2) -36(2) -30(2) C(35) 129(3) 171(3) 334(4) -78(3) -66(2) -25(2) C(36) 105(2) 146(3) 383(4) -60(3) 5(3) -31(2) C(37) 133(3) 174(3) 275(3) -29(3) 62(2) -39(2) C(38) 130(2) 155(3) 186(3) -14(2) 28(2) -35(2) C(39) 121(2) 123(2) 125(2) -46(2) -2(2) -51(2) C(40) 171(3) 150(3) 126(2) -31(2) -9(2) -73(2) C(41) 229(3) 214(3) 129(2) -34(2) -24(2) -94(3) S327
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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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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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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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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 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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Page 277 and 278: Table 2. Atomic coordinates ( x 10
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 287 and 288: Table 5. Anisotropic displacement p
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 301 and 302: Table 3. Selected bond lengths [Å]
Page 303 and 304: C(31)-C(32) 1.499(7) C(32)-C(33) 1.
Page 305 and 306: ___________________________________
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: ___________________________________
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 341 and 342: Table 3. Selected bond lengths [Å]
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)
Page 347 and 348: Table 5. Anisotropic displacement p
Page 349 and 350: C(4A) 499(16) 390(14) 387(15) -71(1
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