V. Cadierno, B. Donnadieu, A. Igau, J.-P. Majoral
FULL PAPER
extracted with pentane (20 mL) and filtered. The volatiles were re-
moved from the solution to give compounds 15a,b as yellow solids.
ethyl ether (3 ϫ 5 mL) to give compound 17 as a yellow solid (72%
yield). – IR (KBr): ν(CϭN) ϭ 1591 cm–1. – 31P{1H} NMR (CD2Cl2):
δ ϭ 83.8 (s). – H NMR (CD2Cl2): δ ϭ 1.08 (d, JHH ϭ 5.9 Hz, 6
H, CH3), 1.19 (d, JHH ϭ 6.9 Hz, 6 H, CH3), 1.37 (d, JHH ϭ 6.9 Hz,
6 H, CH3), 1.47 (d, JHH ϭ 6.9 Hz, 6 H, CH3), 3.94 (m, 2 H, NCH),
4.25 (m, 2 H, NCH), 7.12–8.05 (m, 9 H, CHarom). – 13C{1H} NMR
˜
1
Compound 15a: 72% yield. – IR (KBr): 1571 cm–1 ν˜(CϭN). –
31P{1H} NMR (C6D6): δ ϭ 43.8 [s, P(NiPr2)2], 100.2 (s, PtBu). –
1H NMR (C6D6): δ ϭ 1.09 (d, JHP ϭ 22.9 Hz, 9 H, CCH3), 1.18
(d, JHH ϭ 6.6 Hz, 6 H, CHCH3), 1.20 (d, JHH ϭ 8.3 Hz, 6 H,
(CD2Cl2): δ ϭ 24.7 (br s, CH3), 25.2 (br s, CH3), 50.9 (d, JCP
ϭ
CHCH3), 1.32 (d, JHH ϭ 4.4 Hz, 6 H, CHCH3), 1.35 (d, JHH
4.3 Hz, 6 H, CHCH3), 3.30–3.73 (m, 4 H, NCH), 6.99–7.24 (m, 2
H, CHarom), 7.63 (d, JHH ϭ 7.4 Hz, 1 H, CHarom), 8.44 (d, JHH
7.7 Hz, 1 H, CHarom). – 13C{1H} NMR (C6D6): δ ϭ 24.7 (d, JCP ϭ
6.5 Hz, CHCH3), 25.0 (d, JCP ϭ 6.4 Hz, CHCH3), 27.4 (d, JCP
ϭ
6.3 Hz, NCH), 51.2 (d, JCP ϭ 6.5 Hz, NCH), 123.8, 127.4, 128.3,
128.6, 129.8, 136.3 and 141.7 (s, CHarom), 134.0 (s, i-Ph), 144.7 (d,
JCP ϭ 26.1 Hz, CCSbPh), 146.9 (d, JCP ϭ 10.3 Hz, CSbPh), 194.6
(s, CϭN). – MS (DCI/CH4); m/z: 532 [M ϩ H]ϩ. – C25H37N3PSb
(532.30): calcd. C 56.42, H 7.00, N 7.89; found C 56.30, H 7.11,
N 7.95.
ϭ
ϭ
12.6 Hz, CCH3), 35.2 (dd, JCP ϭ 16.7 Hz, JCP ϭ 3.9 Hz, CCH3),
48.7 (d, JCP ϭ 10.9 Hz, NCH), 126.2 (d, JCP ϭ 8.0 Hz, CHarom),
127.7 (d, JCP ϭ 4.9 Hz, CHarom), 127.9 and 128.2 (s, CHarom), 146.4
Synthesis of Compounds 19, 19’: To a solution of complex 11a
(0.417 g, 0.753 mmol) in toluene (8 mL) was added at 0 °C
Cl2PCH2CH2PCl2 (18) (0.056 mL, 0.376 mmol). The mixture was
stirred at room temperature for 15 min and then evaporated to dry-
ness. The resulting solid residue was extracted with pentane
(15 mL) and filtered. The volatiles were removed from the solution
to give a yellow solid containing an inseparable mixture of two
diastereoisomers 19 and 19’ in a ratio of ca. 2:1 (91% yield). – IR
(KBr): ν˜(CϭN) ϭ 1566 cm–1. – 31P{1H} NMR (CDCl3): δ ϭ 41.4 [s,
P(NiPr2)2 major isomer], 42.6 [s, P(NiPr2)2 minor isomer], 81.5 (s,
PCH2). – 1H NMR (CDCl3): δ ϭ 1.00–1.66 (m, 52 H, CH3 and
CH2), 3.52 (m, 8 H, NCH), 7.25–7.65 (m, 6 H, CHarom), 8.20 (m,
(dd, JCP ϭ 41.8 Hz, JCP ϭ 19.2 Hz, CCPtBu), 152.0 (dd, JCP
24.1 Hz, JCP ϭ 4.2 Hz, CPtBu), 186.2 (pt, JCP ϭ 14.9 Hz, JCP
ϭ
ϭ
14.9 Hz, CϭN). – C23H41N3P2 (421.54): calcd. C 65.53, H 9.80, N
9.96; found: C 65.60, H 9.77, N 10.10. – MS (DCI/NH3); m/z: 422
[M ϩ H]ϩ.
Compound 15b: 69% yield. – IR (KBr): ν˜(CϭN) ϭ 1566 cm–1. –
31P{1H} NMR (C6D6): δ ϭ 44.9 [d, JPP ϭ 6.5 Hz, P(NCy2)2], 99.0
1
(d, JPP ϭ 6.5 Hz, PtBu). – H NMR (C6D6): δ ϭ 0.88–1.93 (m, 49
H, CH2 and CH3), 3.30 (m, 4 H, NCH), 7.09–7.14 (m, 4 H,
CHarom). – 13C{1H} NMR (C6D6): δ ϭ 25.0 (s, CH3), 26.3, 26.7
2 H, CHarom). – 13C{1H} NMR (CDCl3): δ ϭ 23.0 (dd, JCP
28.5 Hz, JCP ϭ 3.9 Hz, CH2), 23.9 (br s, CH3), 24.1 (d, JCP
ϭ
and 27.5 (s, CH2), 27.7 (d, JCP ϭ 6.0 Hz, CH2), 34.7 (d, JCP
ϭ
8.9 Hz, CCH3), 35.6 (br s, CH2), 57.7 (d, JCP ϭ 10.6 Hz, NCH),
58.6 (d, JCP ϭ 8.5 Hz, NCH), 59.8 (d, JCP ϭ 9.7 Hz, NCH), 126.2
(d, JCP ϭ 14.4 Hz, CHarom), 127.6 (d, JCP ϭ 4.3 Hz, CHarom), 127.8
and 129.8 (s, CHarom), 146.6 (dd, JCP ϭ 41.7 Hz, JCP ϭ 20.1 Hz,
CCPtBu), 151.8 (dd, JCP ϭ 26.1 Hz, JCP ϭ 4.8 Hz, CPtBu), 185.9
(pt, JCP ϭ 17.1 Hz,JCP ϭ 17.1 Hz, CϭN). – C34H57N3P2 (569.79):
calcd. C 71.67, H 10.08, N 7.37; found C 71.40, H 9.91, N 7.62.
ϭ
7.1 Hz, CH3), 24.3 (d, JCP ϭ 7.2 Hz, CH3), 47.9 (d, JCP ϭ 10.8 Hz,
NCH), 48.3 (d, JCP ϭ 8.5 Hz, NCH), 48.4 (d, JCP ϭ 8.0 Hz, NCH),
125.5 (d, JCP ϭ 10.3 Hz, CHarom), 126.5 (dd, JCP ϭ 14.9 Hz, JCP ϭ
10.7 Hz, CHarom), 127.2 and 127.4 (s, CHarom), 145.4 (dd, JCP
ϭ
41.4 Hz, JCP ϭ 31.6 Hz, CCPCH2), 151.7 (m, CPCH2), 187.0 (pt,
JCP ϭ 19.7 Hz, JCP ϭ 19.7 Hz, CϭN). – C40H68N6P4 (756.91):
calcd. C 63.47, H 9.05, N 11.10; found C 63.22, H 9.13, N 11.30.
Synthesis of Compound 16a: To a solution of compound 14a
(0.150 g, 0.339 mmol) in toluene (5 mL) was added at room temper-
ature S8 (0.128 g, 0.5 mmol). The mixture was stirred at room tem-
perature for 2 h and then evaporated to dryness. The resulting solid
residue was dissolved in THF (3 mL) and transferred to a silica gel
chromatography column. Elution with pentane gave a yellow band
from which compound 16a was isolated after removal of the solvent
Synthesis of Compound 20: To a solution of compound 14a
(0.115 g, 0.260 mmol) in dichloromethane (5 mL) was added at 0
°C CF3SO3Me (0.029 mL, 0.260 mmol). The mixture was stirred at
room temperature for 15 min and then evaporated to dryness. The
resulting solid residue was washed with pentane (3 ϫ 15 mL) and
dried in vacuo to give compound 20 as a red solid (81% yield). –
IR (KBr): ν˜(CϭN) ϭ 1631 cm–1. – 31P{1H} NMR (CD2Cl2): δ ϭ
(78% yield). – M.p. 121–122 °C (decomp.). – IR (KBr): ν˜(CϭN)
ϭ
1511 cm–1. – 31P{1H} NMR (C6D6): δ ϭ 39.8 [d, JPP ϭ 6.5 Hz,
P(NiPr2)2], 81.9 [d, JPP ϭ 6.5 Hz, P(S)Ph]. – 1H NMR (C6D6): δ ϭ
1.12 (d, JHH ϭ 6.6 Hz, 18 H, CH3), 1.18 (d, JHH ϭ 6.6 Hz, 6 H,
CH3), 3.54 (m, 4 H, NCH), 6.95–7.17 (m, 5 H, CHarom), 7.48 (m,
1 H, CHarom), 7.88 (m, 2 H, CHarom), 8.15 (d, JHH ϭ 7.6 Hz, 1 H,
CHarom). – 13C{1H} NMR (C6D6): δ ϭ 24.5 (d, JCP ϭ 5.9 Hz,
CH3), 24.7 (d, JCP ϭ 7.5 Hz, CH3), 25.0 (d, JCP ϭ 7.0 Hz, CH3),
48.9 (d, JCP ϭ 11.2 Hz, NCH), 49.6 (d, JCP ϭ 10.3 Hz, NCH),
126.0 (pt, JCP ϭ 12.4 Hz, JCP ϭ 12.4 Hz, CHarom), 128.8 (d, JCP ϭ
11.9 Hz, CHarom), 128.9 [d, JCP ϭ 12.7 Hz, o-P(S)Ph], 131.5 [d,
JCP ϭ 11.6 Hz, m-P(S)Ph], 131.8 (d, JCP ϭ 9.8 Hz, CHarom), 132.2
49.2 [d, JPP
ϭ 2.7 Hz, P(NiPr2)2], 70.1 [d, JPP ϭ 2.7 Hz,
P(Me)Ph]. – 1H NMR (CD2Cl2): δ ϭ 1.14–1.32 (m, 24 H, CH3),
2.69 (d, JHP ϭ 14.6 Hz, 3 H, PCH3), 3.60 (m, 4 H, NCH), 7.66–
8.59 (m, 9 H, CHarom). – 13C{1H} NMR (CD2Cl2): δ ϭ 8.7 (dd,
JCP ϭ 61.0 Hz, JCP ϭ 4.0 Hz, PCH3), 23.9 (br s, CH3), 49.5 (d,
JCP ϭ 11.1 Hz, NCH), 49.6 (d, JCP ϭ 13.1 Hz, NCH), 117.8 [dd,
JCP ϭ 93.3 Hz, JCP ϭ 5.0 Hz, CP(Me)Ph], 127.6 (pt, JCP
ϭ
12.6 Hz, JCP ϭ 12.6 Hz, CHarom), 130.3 (d, JCP ϭ 12.9 Hz,
CHarom), 131.8 [d, JCP ϭ 11.0 Hz, o-P(Me)Ph or CHarom], 131.9 [d,
JCP ϭ 8.9 Hz, o-P(Me)Ph or CHarom], 133.5 [d, JCP ϭ 9.3 Hz, m-
P(Me)Ph], 135.5 and 135.8 [s, CHarom and p-P(Me)Ph], 146.8 [dd,
[s, p-P(S)Ph], 132.6 (d, JCP ϭ 2.0 Hz, CHarom), 142.3 [dd, JCP
82.0 Hz, JCP ϭ 2.6 Hz, CP(S)Ph], 144.3 [dd, JCP ϭ 43.9 Hz, JCP
37.3 Hz, CCP(S)Ph], 192.8 (pt, JCP ϭ 21.7 Hz, JCP ϭ 21.7 Hz, Cϭ
N). i-P(S)Ph not observed. – C25H37N3P2S (473.59): calcd. C 63.40,
H 7.87, N 8.87; found C 63.23, H 7.92, N 8.99.
ϭ
JCP ϭ 42.3 Hz, JCP ϭ 32.2 Hz, CCP(Me)Ph], 208.5 (dd, JCP
ϭ
ϭ
29.6 Hz, JCP ϭ 18.2 Hz, CϭN). i-P(Me)Ph not observed. –
C27H40N3O3F3P2S (605.64): calcd. C 53.54, H 6.65, N 6.93; found
C 53.42, H 6.59, N 7.10.
Synthesis of Compound 21: To a solution of compound 16a
Synthesis of Compound 17: To a solution of complex 11a (0.345 g,
(0.100 g, 0.211 mmol) in dichloromethane (5 mL) was added at
0.623 mmol) in toluene (5 mL) was added at room temperature room temperature CF3SO3Me (0.023 mL, 0.211 mmol). The mix-
PhSbCl2 (0.168 g, 0.623 mmol). The mixture was stirred at room
temperature for 15 min and then evaporated to dryness. The re-
sulting solid residue was washed with pentane (3 ϫ 20 mL) and di-
ture was stirred at room temperature for 15 min and then evapor-
ated to dryness. The resulting solid residue was washed with pent-
ane (2 ϫ 15 mL) and dried in vacuo to give compound 21 as a red
420
Eur. J. Inorg. Chem. 2000, 417Ϫ421