Notes
Organometallics, Vol. 24, No. 21, 2005 5183
mg, 0.37 mmol) in 0.6 mL of dichloromethane was heated at
40 °C for 16 h. After that period of time, the solvent was
concentrated to dryness. Addition of diethyl ether (7 mL)
caused the formation of a brown solid. The solution was
decanted and the solid washed with diethyl ether (2 × 3 mL)
and dried in vacuo. Yield: 134 mg (60%). Anal. Calcd for
C22H30BF4OsP: C, 41.36; H, 4.89. Found: C, 41.11; H, 4.38.
IR (Nujol, cm-1): ν(BF4) 1060. 1H NMR (400 MHz, CD2Cl2,
293 K): δ 7.77-6.80 (m, 4H, Ph); 6.15 (dd, 1H, JH-H ) 6.0,
Experimental Section
General Procedures. All reactions were carried out with
rigorous exclusion of air using Schlenk-tube techniques.
Solvents were dried by the usual procedures and distilled
under argon prior to use. The starting material Os(η5-C5H5)-
(CtCPh){[η2-CH2dC(CH3)]PiPr2} (1)9 and DBF4‚D2O16c were
prepared by the published methods. Complex Os(η5-C5H5)(Ct
CC6D5){[η2-CH2dC(CH3)]PiPr2} (1-d5) was prepared analo-
gously to 1 using lithium phenylacetylide-d5 instead of PhCt
CLi.
JH-P ) 2.0, H2); 4.92 (s, 5H, η5-C5H5); 3.82 (ddd, 1H, JH-H
)
6.0, JH-P ) JH-H′ ) 2.0, H1); 3.03 (m, 1H, one of the PCH);
2.55 (m, 1H, one of the PCH); 1.95 (ddd, 1H, JH-P ) 5.6, JH-H
1H, 31P{1H}, and 13C{1H} NMR spectra were recorded on
either a Bruker Avance 300 MHz or a Bruker Avance 400 MHz
instrument. Chemical shifts (expressed in parts per million)
are referenced to residual solvent peaks (1H, 13C{1H}) or
external H3PO4 (31P{1H}). Coupling constants, J, are given in
hertz. Infrared spectra were run on a Perkin-Elmer 1730
spectrometer (Nujol mulls on polyethylene sheets). C, H, and
N analyses were carried out in a Perkin-Elmer 2400 CHNS/O
analyzer. Mass spectral analyses were performed with a VG
Austospec instrument. In LSIMS+ mode, ions were produced
with the standard Cs+ gun at ca. 30 kV, and 3-nitrobenzyl
alcohol (NBA) was used in the matrix.
) 4.4, JH-H ) 2.0, one of the H in CH2); 1.55 (dd, 3H, JH-P
16.0, JH-H ) 7.2, one of the PCHCH3); 1.49 (dd, 3H, JH-P
15.6, JH-H ) 8.0, one of the PCHCH3); 1.47 (dd, 3H, JH-P
16.8, JH-H ) 7.6, one of the PCHCH3); 1.46 (dd, 3H, JH-P
)
)
)
)
13.8, JH-H ) 7.4, one of the PCHCH3); 1.17 (d, 4H, JH-P ) 14.0,
CH3 + 1H of the CH2). 13C{1H} NMR (100.5 MHz, CD2Cl2, 293
K, plus APT, plus HSQC, plus HMBC): δ 165.1 and 164.6
(both s, C3 and C4); 139.8, 129.2, 127.0, and 121.6 (all s, C5,
C6, C7, and C8); 80.0 (s, η5-C5H5); 66.4 (d, JC-P ) 8.5, C2); 52.7
(d, JC-P ) 34.8, C10); 49.4 (d, JC-P ) 23.1, C1); 33.2 (d, JC-P
6.1, C9); 30.2 (d, JC-P ) 14.0, one of the PCH); 25.9 (d, JC-P
)
)
Preparation of [Os(η5-C5H5)(η2-HCtCPh){[η2-CH2dC-
(CH3)]PiPr2}]BF4 (2). A solution of Os(η5-C5H5)(CtCPh){[η2-
CH2dC(CH3)]PiPr2} (1) (155 mg, 0.29 mmol) in 6 mL of diethyl
ether was treated with HBF4‚Et2O (74 µL, 0.53 mmol). An
orange solid was formed immediately. The mixture was stirred
for 10 min, and the solution was decanted. The solid was
washed with diethyl ether (2 × 2 mL) and dried in vacuo.
Yield: 105 mg (60%). Anal. Calcd for C22H30BF4OsP: C, 41.36;
H, 4.89. Found: C, 41.84; H, 5.19. IR (Nujol, cm-1): ν(CtC)
1729; ν(BF4) 1064. 1H NMR (300 MHz, CD2Cl2, 293 K): δ 7.33-
7.07 (5H, Ph); 5.92 (s, 5H, η5-C5H5); 4.09 (s, 1H, HCt); 4.06
31.7, one of the PCH); 23.6 (d, JC-P ) 3.6, C11); 21.7; 19.2, 19.1,
and 18.5 (all s, CH3). 31P{1H} NMR (161.4 MHz, CD2Cl2, 293
K): δ -43.2 (s). MS (LSIMS+): m/z 517 (M+).
Complexes 3-d1 and 3-d5 were prepared similarly starting
from 2-d1 and 2-d5, respectively.
Crystal data for 3: C46H50BOsP, Mw 834.84, yellow, ir-
regular block (0.06 × 0.06 × 0.02 mm), triclinic, space group
P1h, a ) 10.1242(17) Å, b ) 12.635(2) Å, c ) 14.459(2) Å, R )
88.271(4)°, â ) 80.540(3)°, γ ) 89.024(3)°, V ) 1823.4(5) Å3, Z
) 2, Dcalc ) 1.521 g cm-3, F(000) ) 844, T ) 100.0(2) K; µ )
3.573 mm-1. 13 118 measured reflections (2θ ) 3-57°, ω scans
0.3°), 8380 unique (Rint ) 0.0541); min./max. transm factors
) 0.801/0.882. Final agreement factors were R1 ) 0.0581 (6231
observed reflections, I > 2σ(I)) and wR2 ) 0.0977; data/
restraints/parameters ) 8380/0/459; GoF ) 0.831. Largest
peak and hole ) 1.762 and -1.733 e/Å3.
(dd, 1H, JH-P ) 30.2, JH-H ) 3.0, PCdCHtrans P); 2.81 (dd,
to
1H, JH-P ) 8.7, JH-H ) 3.0, PCdCHcis to P); 2.61 (m, 1H, one of
the PCH); 2.32 (d, 3H, JHP ) 8.2, PC(CH3)d); 2.02 (m, 1H,
one of the PCH); 1.73-1.43 (12H, PCHCH3). 13C{1H} NMR
(75.4 MHz, CD2Cl2, 293 K, plus APT, plus HSQC): δ 142.0 (s,
Cipso Ph); 129.4, 127.5, and 126.8 (all s, Ph); 124.5 (s, tCPh);
120.8 (s, HCt); 90.5 (s, η5-C5H5); 52.7 (d, JC-P ) 17.3, PC));
31.4 (d, JC-P ) 5.7, CH2); 30.7 (d, JC-P ) 31.6, one of the PCH);
22.6 (d, JC-P ) 31.0, one of the PCH); 21.5 (d, JC-P ) 6.0, CH3);
19.9 and 17.7 (both s, CH3). 31P{1H} NMR (121.4 MHz, CD2-
Cl2, 293 K): δ 21.9 (br). MS (LSIMS+): m/z 517 (M+); 413 (M+
- PhCtCH).
Acknowledgment. Financial support from the
MCYT of Spain (Project BQU2002-00606, PPQ2000-
0488-P4-02) is acknowledged. M.L.B. thanks the Span-
ish MCYT/Universidad de Zaragoza for funding through
the “Ramo´n y Cajal” program.
Complex 2-d1 was prepared similarly by using DBF4‚D2O
instead of HBF4‚OEt2, whereas 2-d5 was obtained from 1-d5
and HBF4‚OEt2.
Supporting Information Available: Crystallographic
data and bond lengths and angles. This material is available
Preparation of [Os(η5-C5H5)(1,2-dihydro-2-methyl-
naphth-2-yldiisopropylphosphine)]BF4 (3). A solution of
[Os(η5-C5H5)(η2-HCtCPh){[η2-CH2dC(CH3)]PiPr2}]BF4 (2) (200
OM050487Q
Baya, Miguel
