E. Hey-Hawkins et al.
FULL PAPER
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32.3 (C5, C5Ј), 34.2/34.3 (C4, C4Ј), 44.0/44.1 (C6, C6Ј), 49.2/49.9 (C2, (3ϫC14), 43.3/43.7 (d, JCP = 5.7 Hz, C6), 45.1/45.2 (d, JCP
=
C2Ј), 78.9/79.4 (t, JCP = 7.0 Hz, C1, C1Ј), 84.8 (m, JCP + JCP
=
2.6 Hz, 3ϫC12), 48.8/49.1 (d, 3JCP = 4.8 Hz, C2), 77.2/78.4 (d, 2JCP
2
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71.6 Hz, CCB) ppm. 31P{1H} NMR (C6D6): δ = 143.4 ppm. IR
= 13.6 Hz, C1), 77.5/78.0 (d, JCP = 12.3 Hz, C11), 84.4/85.2 (m,
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(KBr): ν = 2957, 2929, 2872 (st, CH , CH), 2627, 2566 (st, BH), 1JCP + 2JCP = 74.8 Hz, CCB) ppm. 31P{1H} NMR (C6D6): δ = 133.1
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1
1454 (st, CH), 1371 (m, CH3), 1179 (w, BC), 1013, 993, 973 (st,
(d, JPP = 143.5 Hz), 137.5 (d, JPP = 143.5 Hz) ppm. IR (KBr): ν
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POC), 864 (st, PO); not assigned: 3417 (w, br), 1943, 1857, 1737, = 2919, 2853, 2623, 2595, 2567, 1455, 1369, 1352, 1301, 1238, 1184,
1605 (w), 1496, 1343 (m); 1295, 1269, 1238, 1155 (w), 1077 (m),
924, 818, 802 (st), 730 (m), 695, 677, 628, 596, 551, 528, 484, 465,
425 (w). MS (DEI pos.): m/z (%) = 824.7 (1.7) [M+], 550.1 (1.2)
1104, 1058, 1012, 990, 967, 946, 860, 825, 768, 627, 583, 552,
481 cm–1. MS (EI pos., 14 eV): m/z (%) = 816.6 (100) [M+ + H].
C42H78B10O4P2 (817.12): calcd. C 61.7, H 9.62; found C 61.2, H
9.57.
[M+ – 2 C10H19], 410.2 (28.4) [M+ – 3 C10H19], 273.1 (100) [M+
–
4 C10H19]. C42H86B10O4P2 (825.19): calcd. C 61.5, H 10.30; found
C 62.5, H 10.50.
[1,2-Bis[bis(4-tert-butylphenyloxy)phosphanyl]-closo-dicarbaborane-
(12)]tetracarbonylmolybdenum(0) (7): 5 (0.2 g, 0.3 mmol) in 10 mL
n-hexane, [Mo(CO)4(nbd)] (0.09 g, 0.3 mmol) 10 mL n-hexane.
1,2-Bis[bis(4-tert-butylphenyloxy)phosphanyl]-closo-dicarbabor-
ane(12) (5): 1,2-Dicarba-closo-doedcaborane(12) (0.44 g, 3 mmol) Crystallisation from n-hexane; yield 0.43 g (85%); m.p. 262–278 °C
in 30 mL of diethyl ether, nBuLi (2.6 mL) in n-hexane (2.4 ), 2
(2.3 g, 0.63 mmol) in 60 mL of diethyl ether. Crystallisation from
n-hexane/toluene; yield 1.85 g (77%); m.p. 119–121 °C. 1H NMR
(C6D6): δ = 1.07 (s, 36 H, CH3), 2.20–3.90 (br. m, 10 H, HB), 6.93
(decomp.). 1H NMR (C6D6): δ = 1.10 (s, 36 H, CH3), 2.20–3.90
(br. m, 10 H, HB), 7.08 (s, 16 H, CH) ppm. 11B{1H} NMR (C6D6):
δ = –1.5 (br. s, 2 B), –3.2 (br. s, 2 B), –10.7 (br. s, 6 B) ppm. 13C{1H}
NMR (C6D6): δ = 31.0 (C-(CH3)3), 34.0 (C-(CH3)3), 89.4 (m, CCB),
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(m, 16 H, CH) ppm. 11B{1H} NMR (C6D6): δ = 1.4 (br. s, 2 B), 121.7 (d, JCP = 4.0 Hz, Cortho), 126.8 (Cmeta), 148.8 (Cpara), 149.8
–6.4 (br. s, 2 B), –9.5 (br. s, 4 B) ppm. 13C{1H} NMR (C6D6): δ = (t, JCP = 5.8 Hz, Cipso), 203.9 (t, JCP = 10.8 Hz, COaxial), 209.8
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2
31.1 (C-(CH3)3), 34.0 (C-(CH3)3), 82.2 (m, JCP + JCP = 69.0 Hz,
(dd, 2JCP = 12.5, 2JCP = 42.1 Hz, COequatorial) ppm. 31P{1H} NMR
3
CCB), 119.2 (t, JCP = 4.0 Hz, Cortho), 126.8 (Cmeta), 147.2 (Cpara), (C D ): δ = 199.7 ppm. IR (KBr): ν = 2965, 2907, 2871, 2619, 2578,
˜
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151.7 (t, JCP = 5.8 Hz, Cipso) ppm. 31P{1H} NMR (C6D6): δ = 2054, 1983, 1958, 1601, 1507, 1464, 1397, 1365, 1265, 1216, 1204,
161.2 ppm. IR (KBr): ν = 2964, 2905, 2869, 2615, 2572, 1602, 1508,
1170, 1109, 1079, 1016, 903, 840, 814, 753, 677, 644, 585, 560, 529,
cm–1. MS (EI pos., 40 eV): m/z (%) = 1009.4 (7.5) [M+], 981.4 (6.3)
[M+ – CO], 925.3 (100) [M+ – 3CO], 897.5 (25.8) [M+ – 4CO].
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1463, 1365, 1267, 1227, 1203, 1170, 1111, 1079, 1014, 894, 843,
833, 761, 731, 552 cm–1. MS (EI pos., 40 eV): m/z (%) = 800 (1.0)
[M+], 743 (1.2) [M+ – C4H9], 651 (100) [M+ – C10H13O], 502 (14.4) C46H62B10MoO8P2 (1008.98): calcd. C 54.8, H 6.19; found C 52.4,
[M+ – 2 C10H13O]. C42H62B10O4P2 (801.00): calcd. C 65.4, H 8.10;
H 6.33.
found C 65.3, H 8.06.
{1,2-Bis[bis(–)-menthyloxyphosphanyl]-closo-dicarbaborane(12)}-
tetracarbonylmolybdenum(0) (8): Compound 4 (0.25 g, 0.3 mmol) in
10 mL n-hexane, [Mo(CO)4(nbd)] (0.09 g, 0.3 mmol) in 10 mL n-
hexane. Crystallisation from n-hexane; yield 0.44 g (87%); m.p.
236–257 °C (decomp.). 1H NMR (C6D6): δ = 0.71 (m, 4 H, H4),
0.95 (m, 40 H, H3, H8, H9, H10), 1.46 (m, 20 H, H2, H3, H4, H5,
(RP,RP)-1,2-Bis[1-adamantyloxy-(–)-menthyloxyphosphanyl]-closo-
dicarbaborane(12) [(RP,RP)-6]: 1,2-Dicarba-closo-dodecaborane(12)
(0.29 g, 2 mmol) in 30 mL of diethyl ether, nBuLi (1.7 mL) in n-
hexane (2.4 ), 3 (1.6 g, 0.42 mmol) in 50 mL of diethyl ether. The
diastereomers could be separated by fractional crystallisation from
n-hexane; yield 0.48 g (31%); m.p. 234–236 °C. H NMR (C6D6): H6), 2.20–3.90 (br. m, 10 H, HB), 2.50 (m, 4 H, H6), 2.75 (m, 4 H,
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δ = 0.76 (m, 4 H, H3, H4), 0.91 (m, 18 H, H8, H9, H10), 1.25 (m, 4
H7), 4.29 (m, 1 H, H1) ppm. 11B{1H} NMR (C6D6): δ = –1.9 (br.
H, H5, H6), 1.47 (m, 18 H, H2,H3, H4, H14), 2.05 (m, 18 H, H12, s, 2 B), –4.2 (br. s, 2 B), –11.0 (br. s, 4 B) ppm. 13C{1H} NMR
H13), 2.20–4.20 (br. m, 10 B, HB), 2.40 (m, 2 H, H6), 2.55 (m, 2 H, (C6D6): δ = 16.7/16.8 (C8, C8Ј), 21.2/21.3 (C9, C9Ј), 21.8/22.0 (C10,
H7), 3.71 (m, 2 H, H1) ppm. 11B{1H} NMR (C6D6): δ = –0.5 (br. C10Ј), 23.1/23.4 (C3, C3Ј), 24.8/24.9 (C7, C7Ј), 31.9/32.0 (C5, C5Ј),
s, 2 B), –6.5 (br. s, 2 B), –10.3 (br. s, 6 B) ppm. 13C{1H} NMR
33.6/34.0 (C4, C4Ј), 43.4/45.2 (C6, C6Ј), 49.0/49.6 (C2, C2Ј), 80.6/82.6
(C6D6): δ = 16.5 (C8), 21.0 (C9), 22.1 (C10), 23.1 (C3), 25.0 (C7), (C1, C1Ј), 90.9 (m, CCB), 208.4 (t, JCP = 11.3 Hz, COaxial), 213.3
2
31.1 (3·C13 in ada), 31.5 (C5), 34.1 (C4), 35.7 (3·C14 in ada), 43.9
(dd, 2JCP = 13.1, 2JCP = 39.2 Hz, COequatorial) ppm. 31P{1H} NMR
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(t, JCP = 3.8 Hz, C6), 45.0 (t, JCP = 4.4 Hz, 3·C12 in ada), 49.0 (C D ): δ = 189.5 ppm. IR (KBr): ν = 2958, 2930, 2870, 2628, 2573,
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(C2), 77.1 (t, 2JCP = 7.4 Hz, C1), 77.2 (t, 2JCP = 6.7 Hz, C11 in ada),
2037, 1952, 1925, 1457, 1371, 1077, 1008, 986, 961, 931, 864, 822,
769, 629, 599, 591, 569, 546, 435 cm–1. MS (ESI neg., CH2Cl2/
CH3CN): m/z (%) = 1033.6 (100) [M–], 1056.6 (52) [M + Na]–.
1
85.1 (m, JCP + 2JCP = 67.2 Hz, CCB) ppm. 31P{1H} NMR (C6D6):
δ = 130.7 ppm. IR (KBr): ν = 2958, 2882, 2623, 2579, 1474, 1454,
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1391, 1364, 1306, 1262, 1229, 1112, 1074, 1007, 990, 976, 942, 923, C46H86B10MoO8P2 (1033.17): calcd. C 53.5, H 8.39; found C 54.8,
900, 804, 742, 724, 626, 478 cm–1. MS (ESI pos., CHCl3/CH3OH):
m/z (%) = 818.6 (37.3) [M+ + H], 840.6 (100) [M+ + Na], 856.6
(12.8) [M+ + K]. C42H78B10O4P2 (817.12): calcd. C 61.74, H 9.62;
found C 61.54, H 9.69.
H 8.71.
9: Compound 5 (0.08 g, 0.1 mmol) in 5 mL of CH2Cl2, [{Rh(µ-
Cl)(cod)}2] (0.025 g, 0.05 mmol) in 2 mL of CH2Cl2. Crystallisation
from toluene; yield 0.08 g (85%); m.p. 306–308 °C (decomp.). 1H
NMR (C6D6): δ = 1.15 (s, 72 H, CH3), 2.50–3.50 (br. m, 20 H,
(RP,SP)-1,2-Bis[1-adamantyloxy-(–)-menthyloxyphosphanyl]-closo-
dicarbaborane(12) [(RP,SP)-6]: The diastereomers could be sepa-
rated by fractional crystallisation from n-hexane; yield 0.52 g
HB), 7.09 (d, JHH = 8.4 Hz, 16 H, CH), 7.39 (d, JHH = 8.4 Hz,
16 H, CH) ppm. 11B{1H} NMR (C6D6): δ = –1.7 (br. s, 6 B), –9.5
(br. s, 4 B) ppm. 13C{1H} NMR (C6D6): δ = 31.1 [C-(CH3)3], 34.0
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(33%); m.p. 241–242 °C. H NMR (C6D6): δ = 0.85 (m, 2 H, H4),
0.94 (m, 20 H, H3, H8, H9, H10), 1.30 (m, 4 H, H5, H6), 1.47 (m, [C-(CH3)3], 89.4 (m, CCB), 120.8 (Cortho), 126.3 (Cmeta), 147.5
18 H, H2, H3, H4, H5, H6, H14), 2.04 (m, 18 H, H12, H13), 2.20– (Cpara), 149.8 (Cipso) ppm. 31P{1H} NMR (C6D6): δ = 152.6 (d,
4.20 (br. m, 10 B, HB), 2.56 (m, 2 H, H6), 3.02 (m, 2 H, H7), 3.77
1JRhP = 284.3 Hz) ppm. IR (KBr): ν = 2964, 2905, 2869, 2614,
˜
(m, 2 H, H1) ppm. 11B{1H} NMR (C6D6): δ = –0.2 (br. s, 2 B), 2578, 1601, 1507, 1463, 1394, 1364, 1265, 1205, 1169, 1110, 1082,
–6.8 (br. s, 2 B), –10.2 (br. s, 6 B) ppm. 13C{1H} NMR (C6D6): δ
= 16.0/16.5 (C8), 21.0/21.1 (C9), 22.0/22.1 (C10), 22.7/23.1 (C3),
24.9/25.0 (C7), 31.1 (3ϫC13), 31.6/31.8 (C5), 33.9 (C4), 35.7/35.8
1015, 923, 862, 843, 832, 808, 753, 681, 649, 635, 545, 524,
488 cm–1. MS (EI pos.): m/z (%) = 939.4 (12.7) [M+/2], 903.4 (35.3)
[M+/2 – Cl], 770.3 (17.9) [M+/2 – Cl – C10H13], 754.3 (100) [M+/2 –
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Eur. J. Inorg. Chem. 2009, 2776–2788