Notes
Organometallics, Vol. 18, No. 9, 1999 1797
They were given isotropic thermal parameters 20% higher
than those of the carbon to which they were attached. All non-
hydrogen atoms were refined anisotropically. The final R (Rw)
values were 0.0387 (0.0389) for 2872 reflections used with the
criterion I > σ(I), and 416 variables were refined. The
calculation were carried out with the aid of CRYSTALS. The
drawing of the molecule was realized with CAMERON with
thermal ellipsoids at the 50% probability level.
tion onto the alkenyl ligand. This observation supports
the view that the facile protonation of 5 could occur
indifferently in toluene or in THF, in contrast to the
release of 3 observed in THF.
Extension of this work to include the reactivity of
vanadocene Cp2V with various unsaturated main group
element species is under way.
P r ep a r a tion of 6-E/Z a n d 7-E/Z. To a solution of 1 (0.182
g, 0.270 mmol) in toluene (3 mL), at -78 °C, was added HCl‚
OEt2 (552 µL; 1 M). The mixture was then stirred for 2 h at
room temperature. In the course of the reaction, a green
precipitate, identified after filtration by EPR and chemical
analysis as Cp2VCl2, appeared with the formation of 6-E/Z in
1:1 ratio as monitored by 31P{1H} NMR spectroscopy. After
addition of sulfur (10 equiv) to 6-E/Z, the resulting solution
was refluxed for 16 h and then evaporated to dryness. The
corresponding products 7-E/Z were separated by chromatog-
raphy (silica gel eluted with pentane/THF 95/5) in 60% total
isolated yield.
Exp er im en ta l Section
All manipulations were conducted under an argon atmos-
phere using either standard Schlenk tube or glovebox tech-
niques. Nuclear magnetic resonance (NMR) spectra were
recorded on Bruker MSL 400, AM-250, AC-200, and AC-80
Fourier transform spectrometers. Positive chemical shifts are
downfield relative to Me4Si (1H, 13C) or H3PO4 (31P) references,
respectively. Mass spectrum analyses were performed by the
analytical service of the Laboratoire de Chimie de Coordination
(LCC) of the CNRS. Magnetic susceptibility measurements
were carried out using Faraday’s method. EPR spectra were
recorded on a Bruker ER 200T spectrometer. Infrared spectra
were recorded in solution (5 mg of 5 in 0.150 mL of THF-d8 or
toluene-d8) or in Nujol on a Perkin-Elmer FT-IR spectropho-
tometer. The reference spectrum of the solvents was sub-
tracted. Solvents were freshly distilled from sodium/benzophe-
none ketyl (THF, toluene) or lithium aluminum hydride
(pentane). C6D6 was treated with CaH2, distilled, and stored
under argon. HCl-OEt2 was purchased from Aldrich. Cp2V9a
7-E: (Rf ) 0.49), DCI/CH4, m/e ) 513 ([M + 1]+). 31P{1H}
NMR (C6D6): δ 18.6 ppm. 1H NMR (C6D6): δ 8.35 (dd, 3J (H,P)
3
4
) 24.7 Hz, J (H,H) ) 16.4 Hz, 1H, CHPh); 7.67 (d, J (H,P) )
4.7 Hz, 2H, CHAr); 7.18-7.02 (m, 7H, CHPh); 6.92-6.80 (m,
2
3
3H, CHPh), 6.85 (dd, J (H,P) ) 21.7 Hz, J (H,H) ) 16.4 Hz,
1H, PCH); 1.50 (s, 18H, p-tBu); 1.37 (s, 9H, o-tBu). 13C{1H}
NMR (C6D6): δ 152.4 (d, 2J (C,P) ) 4.6 Hz, o-CAr); 144.7 (d,
2J (C,P) ) 7.8 Hz, CHPh); 136.1 (d, J (C,P) ) 20.0 Hz, i-CPh),
3
132.5 (d, J (C,P) ) 1.0 Hz, CHPh); 130.1, 130.0, 129.9, 129.4,
128.9, 126.3 (s, CPhH); 125.6 (d, 3J (C,P) ) 13.7 Hz, m-CAr);
102.2 (d, 2J (C,P) ) 26.1 Hz, tCPh); 91.3 (d, J (C,P) ) 150.8
Hz, PCt); 35.3, 31.5, 30.9 (s, CCH3), PCH not identified. Anal.
Calcd for C34H41PS: C, 79.64; H, 8.06. Found: C, 79.51; H, 7.94.
7-Z: (Rf ) 0.24), DCI/CH4, m/e ) 513 ([M + 1]+). 31P{1H}
NMR (C6D6): δ 9.8 ppm. 1H NMR (C6D6): δ 7.62 (d, 4J (H,P) )
5.4 Hz, 2H, CHAr); 7.17-6.85 (m, 10H, CHPh); 6.80 (dd, 3J (H,P)
) 20.0 Hz, 3J (H,H) ) 13.6 Hz, 1H, CHPh); 6.56 (dd, 2J (H,P) )
46.5 Hz, 3J (H,H) ) 13.6 Hz, 1H, PCH); 1.49 (s, 18H, o-tBu);
1.31 (s, 9H, p-tBu). 13C{1H} NMR (C6D6): δ 152.4 (d, J (C,P) )
4.5 Hz, o-CAr); 140.9 (d, 2J (C,P) ) 5.4 Hz, CHPh); 136.4 (d,
2J (C,P) ) 13.1 Hz, i-CPh); 135.7 (d, J (C,P) ) 7.0 Hz, CPh); 135.3
9b
and Ar-P(CtCPh)2 (Ar ) 2,4,6-t-Bu3(C6H2)) were prepared
according to the literature.
Syn th esis of Cp 2V(η2-P h CdC)P (CtCP h )Ar , 5. A solu-
tion of 3 (0.530 g, 1.10 mmol) in 10 mL of pentane was added
slowly to a pentane solution (20 mL) of Cp2V (0.200 g, 1.10
mmol). After 1 h stirring, the solution was left overnight to
give black crystals of 5, which were collected by filtration and
dried in vacuo (0.510 g, 70% yield). Anal. Calcd for C44H49PV:
C, 80.02; H, 7.42; V, 7.73. Found: C, 79.82; H, 7.32; V, 7.80.
Cr ysta l Str u ctu r e Da ta for 5. Crystallographic data:
C
44H49PV; Mw ) 659.79; triclinic; space group P1h; unit cell a
) 11.083(5) Å, b ) 11.788(2) Å, c 15.414(2) Å, R ) 76.34(2)°, â
) 79.31(3)°, γ ) 74.87(3)°; V ) 1872.6(9) Å3; Fcalcd ) 1.17 cm-3
1
(d, J (C,P) ) 92.6 Hz, i-CAr); 132.5 (d, J (C,P) ) 1.2 Hz, CPh);
;
µ ) 3.25 cm-1; crystal dimensions 0.4 × 0.3 × 0.2 mm3. The
X-ray diffraction data were collected at 293 K on an Enraf
Nonius CAD4 diffractometer using graphite-monochromatized
Mo KR radiation. A total of 7520 reflections were measured
(7228 independent) with Raverage ) 0.03. The structure was
solved using direct methods (SIR92) and refined by least-
squares procedures on Fobs. H atoms were located on difference
Fourier maps, but they were introduced into the calculation
in idealized positions (d(C-H) ) 0.96 Å), and their atomic
coordinates were recalculated after each cycle of refinement.
131.5 (d, J (C,P) ) 98.6 Hz, PCH); 130.0 (d, J (C,P) ) 1.0 Hz,
CPh); 131.6, 129.0, 128.9, 126.3 (s, CPh); 121.9 (d, J (C,P) )
3.8 Hz, m-CAr); 35.3, 31.5, 30.8 (s, CCH3). Anal. Calcd for
C
34H41PS: C, 79.64; H, 8.06. Found: C, 79.48; H, 7.95.
Ack n ow led gm en t . Thanks are due to CNRS
(France) for financial support.
Su p p or t in g In for m a t ion Ava ila b le: Listing of atomic
coordinates, hydrogen positional parameters, isotropic and
anisotropic displacement parameters, and complete bond
distances and angles. This material is available free of charge
(9) (a) Eisch, J . J .; King, R. B. Organometallic Synthesis of Transi-
tion Metal Compounds; Academic Press: New York, 1965. (b) Charrier,
C.; Simonnin, M. P.; Chodkiewicz, W.; Cadiot, P. C. R. Acad. Sci. 1964,
1537.
OM980983X