Article
Organometallics, Vol. 28, No. 20, 2009 6035
0.28 mL (0.44 mmol) of n-butyllithium and 0.06 mL (0.44 mmol)
of diisopropylamine) in 10 mL of diethyl ether cooled to -80 °C
was slowly addded a solution of 221 mg (0.4 mmol) of 1a and
65 μL (0.4 mmol) of 12-crown-4 in 5 mL of diethyl ether. Then a
solution of 112 mg (0.44 mmol) of iodine in 5 mL of diethyl ether
was dropped into the phosphinidenoid complex solution, and
the reaction mixture was stirred for 3.5 h while gently warming
to þ10 °C. The solvent was removed under vacuum. The
product was extracted five times with 3 mL of n-pentane. After
evaporation, the yellow solid was dissolved with 2 mL of
n-pentane and cooled to -80 °C. The precipitated crystals were
separated from the solution by a syringe. The residue was dried
under vacuum.
was slowly added a solution of 550 mg (1 mmol) of 1a and 180 μL
(1.1 mmol) of 12-crown-4 in 10 mL of diethyl ether. After 5 min
an in situ prepared solution of iodo phenylacetylene was added.
The reaction mixture was stirred for 2 h while slowly warming to
0 °C. Then the solvents were evaporated, and the residue was
suspended with 10 mL of diethyl ether. The products were
adsorbed on Al2O3 purified by column chromatography
(Al2O3, -20 °C) using (1) petroleum ether and (2) a mixture of
petroleum ether and diethyl ether (19:1 and 18:2). The second
fraction contained 8, which after removal of the solvents was
obtained as a pale yellow solid and was subsequently washed
with 2 mL of n-pentane. 9 was obtained from the third and
fourth fraction as a sunflower yellow powder, which was
subsequently washed three times with 2 mL of n-pentane to
yield the pure product as a pale yellow powder.
6a: yellow solid; yield 195 mg (0.29 mmol, 72%); mp 64-
69 °C (dec); NMR spectroscopy (C6D6, 30 °C): 1H NMR [ppm]
δ 0.21 (s, 9H, SiMe3), 0.27 (d, 4J(P,H) = 0.57 Hz, 9H, SiMe3),
2.55 (d, 2J(P,H)=5.19 Hz, 1H, PCH); 13C{1H} NMR [ppm] δ
0.0 (d, 3J(P,C) = 4.5 Hz, SiMe3), 1.0 (d, 3J(P,C)=3.2 Hz, SiMe3)
39.5 (d, 1J(P,C) = 31.7 Hz, PC), 195.8 (dSat, 1J(W,C) = 128.0
Hz, 2J(P,C) = 7.1 Hz, cis-CO), 196.8 (dSat, 2J(P,C) = 44.3 Hz,
8: pale yellow solid; yield 74 mg (0.095 mmol, 10%); mp
1
132-135 °C (dec); H NMR [ppm] δ 0.30 (s, 18H, (SiMe3)2),
1.69 (d, 1H, 2J(P,H) = 4.96 Hz, PCH), 7.40 (d, 1H, 2J(P,H) =
16.8 Hz, PCH), 7.45 (m, 2H, Ph), 7.28 (m, 3H, Ph); 13C{1H}
NMR [ppm] δ 1.6 (d, 1J(P,C)=4.1 Hz, SiMe3), 2.2 (d, 1J(P,C) =
2.7 Hz, SiMe3), 33.1 (d, 1(P,C) = 9.1 Hz, P-CH), 112.6 (d, 3J(P,
C) = 3.3 Hz, i-Ph), 127.6 (s, o-Ph), 127.7 (s, m-Ph), 128.8 (s, p-
Ph), 139.8 (d, 2J(P,C) = 4.4 Hz, PCHCIPh), 140.7 (d, 1J(P,C) =
11.0 Hz, PCHCIPh), 195.7 (d, 1J(W,C) = 127.6 Hz, 2J(P,C) =
1
trans-CO); 31P{1H} NMR [ppm] δ 78.2 (sSat, J(W,P)=311.5
Hz); MS m/z (%) 675.9 (4) [(M)þ]; FTIR (KBr) ν(CO) ν~=1951
(s), 1997 (m), 2079 (m) [cm-1]. Anal. Calcd: C 21.30, H 2.83.
Found: C 21.50, H 3.04. X-ray crystallographic analysis: Sui-
table pale yellow single crystals were obtained from concen-
trated n-pentane solutions. C12H19ClIO5PSi2W; crystal size 0.54
2
7.1 Hz, cis-CO), 197.8 (d, J(P,C)=33.0 Hz, trans-CO) ppm;
31P{1H} NMR [ppm] δ 89.7 (dSat, 1J(W,P) = 283.6 Hz); MS m/z
(%) 777.9 (1) [(M)þ]; FTIR (KBr) ν(CO) ν~=2074 (m), 1984 (m),
1923 (s); ν(CdC): 1598 (w), 1967 (w), 1581 (w) [cm-1]. Anal.
Calcd C 30.85, H 3.24. Found: C 30.53, H 3.32.
3
˚
ꢀ 0.16 ꢀ 0.10 mm , monoclinic, P21/n, a = 14.7403(4) A, b=
˚
˚
9.6381(2) A, c = 15.3230(3) A, R = 90°, β = 101.3970(10)°, γ =
3
˚
90°, V=2133.99(8) A , Z=4, 2θmax=55°, collected (indepen-
dent) reflections = 20 403 (4838), Rint=0.0856, μ = 7.188 mm1,
218 refined parameters, R1 (for I > 2σ(I)) = 0.0394, wR21 (for
all data) = 0.1042, max./min. residual electron density =1.749/
9: pale yellow solid; yield 159 mg (0.19 mmol, 19%); mp
116-120 °C (dec); 1H NMR [ppm]: δ 0.5 (s, 18H, (SiMe3)2), 7.4
(m, 10H, CCPh 2ꢀ); 13C{1H} NMR [ppm] δ 3.5 (s, (SiMe3)2),
85.5 (d, 1J(P,C) = 73.9 Hz, P-CC-Ph), 109.1 (d, 2J(P,C) = 13.7
Hz, P-CC-Ph), 120.7 (s, ipso-Ph-C), 128.3 (s, ortho-Ph-CH),
129.9 (s, para-Ph-CH), 131.7 (s, meta-Ph-CH), 198.0 (d, 2J(P,C)
= 6.6 Hz, cis-CO), 200.1 (d, 2J(P,C) = 28.6 Hz, trans-CO);
31P{1H} NMR [ppm] δ 19.2 (dSat, 1J(W,P) = 265.8 Hz); MS m/z
(%): 715.1 (0.5) [(M)þ - I]; FTIR (KBr) ν(CO) ν~ = 2070 (m),
1981 (m), 1924 (s); ν(CtC) 2163 (m) [cm-1]. Anal. Calcd: C
39.92, H 3.35. Found: C 39.77, H 3.42.
3
˚
-4.643 e A .
Synthesis of Complex 6b. To a solution of 0.5 mmol of lithium
diisopropylamide (LDA, freshly prepared from 0.32 mL (0.5
mmol) of n-butyllithium and 0.07 mL (0.5 mmol) of
diisopropylamine) in 5 mL of diethyl ether cooled to -80 °C
was slowly added a solution of 221 mg (0.42 mmol) of 1b and
68 μL (0.42 mmol) of 12-crown-4 in 5 mL of diethyl ether. Then a
solution of 107 mg (0.42 mmol) of iodine in 1 mL of diethyl ether
was dropped into the phosphinidenoid complex solution, and
the reaction mixture was stirred for 3.5 h while gently warming
to 0 °C. The liquid was filtered from the solid and dried under
vacuum. The raw product was purified further by column
chromatography (Al2O3, -20 °C) using n-pentane.
X-ray Crystallographic Analysis. Suitable pale yellow single
crystals were obtained from concentrated diethyl ether solu-
tions. C28H28IO5PSi2W; crystal size 0.44 ꢀ 0.40 ꢀ 0.39 mm3,
˚
˚
monoclinic, P21/n, a = 12.4156(3) A, b=14.4943(5) A, c =
˚
17.6597(5) A, R=90°, β = 91.404(2)°, γ=90°, V = 3177.00(16)
3
˚
6b: orange solid; yield 161 mg (0.25 mmol, 59%); mp 104 °C
(dec); NMR spectroscopy (C6D6, 30 °C): 1H NMR [ppm] δ 1.37
(d, J(P,H) = 16.4 Hz, 3H, Cp*(C1)-CH3), 1.56 (ddq, J(P,H) =
7.4 Hz, J(H,H) = 3.2 Hz, J(H,H) = 1.1 Hz, 6H, Cp*-CH3), 1.75
(br s, 3H, Cp*-CH3), 1.79 (br s, 3H, Cp*-CH3); 13C{1H} NMR
[ppm] δ 10.4 (d, J(P,C) = 2.6 Hz, Cp*-CH3) 10.5 (d, J(P,C) =
2.6 Hz, Cp*-CH3) 11.8 (d, J(P,C) = 0.6 Hz, Cp*-CH3) 12.1 (s,
Cp*-CH3) 16.5 (d, 2J(P,C)=6.8 Hz, Cp*(C1)-CH3) 65.5 (d, 1J(P,
C) = 19.4 Hz, Cp*(C1)), 133.5 (d, J(P,C) = 3.2 Hz, Cp*), 133.6
(d, J(P,C) = 1.3 Hz, Cp*), 145.0 (d, J(P,C)=10.0 Hz, Cp*),
145.1 (d, J(P,C)=9.7 Hz, Cp*), 195.6 (dSat, 2J(P,C) = 7.1 Hz,
A , Z = 4, 2θmax =55°, collected (independent) reflections =
31 420 (7154), Rint=0.0535, μ=4.767 mm1, 349 refined para-
meters, R1 (for I > 2σ(I)) = 0.0263, wR21 (for all data) =0.0685,
3
˚
max./min. residual electron density=1.726/-1.684 e A .
Acknowledgment. Financial support by the DFG
(STR 411/26-1), the COST action cm0802, the DAAD
PPP Program “Acciones Integradas”, and Ministerio de
ꢁ
Ciencia e Innovacion (HA-2005-0141) is gratefully ac-
knowledged.
cis-CO), 196.7 (dSat,
2J(P,C) = 44.9 Hz, trans-CO); 31P{1H}
Supporting Information Available: CIF files giving X-ray
crystallographic data for 6a and 9. This material is available
lographic data of 6a and 9 have also been deposited at the
Cambridge Crystallographic Data Centre under the numbers
CCDC-729255 (6a) and CCDC-729255 (9). These data can be
obtained free of charge from the Cambridge Crystallographic
1
NMR δ 98.6 (sSat, J(W,P)=309.0 Hz); MS m/z (%) 652 (1)
[(M)þ]; FTIR (KBr; ν(CO)) ν~=1939 (s), 1995 (m), 2078 (m)
[cm-1]. Anal. Calcd: C 27.61, H 2.32. Found: C 28.26, H 2.50.
Synthesis of Complexes 8 and 9. To a solution of 1.1 mmol of
lithium diisopropylamide (LDA, freshly prepared from 0.69 mL
(1.0 mmol) of n-butyllithium and 0.14 mL (1.0 mmol) of
diisopropylamine) in 10 mL of diethyl ether cooled to -90 °C