J. Hydrio et al. / Journal of Organometallic Chemistry 595 (2000) 261–267
265
NMR (CDCl3): l 0.72 (t, 3JHH=7.3 Hz, 3H, Me),
0.92 (t, JHH=7.3 Hz, 3H, Me), 1.19 (m, 2H, CH2),
100%). Anal. Calc. for C28H29PS: C, 78.47; H,6.82;
S,7.48. Found: C,78.24; H, 6.74; S, 7.13.
3
1.53 (m, 2H, CH2), 2.30 (m, 2H+1H, CH2), 2.60 (m,
1H, CH2), 6.96 (m, 5H, Ph), 7.23 (m, 5H, Ph), 7.32
(m, 5H, Ph). 13C-NMR (CDCl3): l 14.23 (s, CH3),
14.47 (s, CH3), 22.24 (d, 2JCP=22.5 Hz,
CH2ꢀCH2ꢀCH3), 23.10 (s, CH2ꢀCH2ꢀCH3), 30.36 (s,
4.2. X-ray data collection and structure determination
Data for 5a, 5c and 4a were collected on a Stoe
IPDS diffractometer equipped with a graphite oriented
monochromator using Mo–Ka radiation (u=0.71073).
The final unit cell parameters were obtained by the
least-squares refinement of 5000 reflections. Data for
5b were collected on an Enraf–Nonius CAD4 diffrac-
tometer and the final unit cell was derived from the
refinement of 25 well centered reflections. In all cases,
only statistical fluctuations were observed in the inten-
sity monitors over the course of the data collections.
The four structures were solved by direct methods
CH2ꢀCH2ꢀCH3),
30.82
(d,
3JCP=17.8
Hz,
CH2ꢀCH2ꢀCH3), 125.68–133.86 (Ph), 136.78 (d,
2JCP=17.3 Hz, CꢀPh), 138.65 (s, CꢀPh), 146.14 (s,
2
CꢀPr), 147.55 (d, JCP=8.0 Hz, CꢀPr). MS m/z (rel.
int.) 397 ( MH+, 100%).
2,3-Dimethyl-4,5-diphenyl-1-phenylphosphole-sulfide
(5a): (36%). Orange crystals were obtained by diffu-
sion of pentane into a dichloromethane solution.
m.p.=143–145°C. 31P-NMR (CDCl3): l 56.3. 1H-
NMR (CDCl3): l 1.87 (s, 3H, Me), 1.96 (d, 3H,
3JHP=14 Hz, Me), 6.90–7.56 (m, 13H, Ph), 7.88 (m,
(SIR92) [8] and refined by least-squares procedures on
Fo. All H atoms attached to carbon were introduced
in the calculation in idealized positions (d(CH)=0.96
2
2H, Ph). 13C-NMR (CDCl3): l 9.90 (d, JCP=14 Hz,
3
CH3), 15.10 (d, JCP=14.5 Hz, CH3), 127.50–132.40
,
A) and their atomic coordinates were re-calculated
(Ph), 132.50 (d, 1JCP=79 Hz, CꢀCH3), 134.80 (d,
1JCP=77.6 Hz, CꢀPh), 145.40 (d, 2JCP=22.8 Hz,
CꢀMe), 151.60 (d, 2JCP=22.5 Hz, CꢀPh). MS m/z
(rel. int.) 373 (MH+, 100%). Anal. Calc. for C24H21PS:
C, 77.39; H, 5.68; S, 8.61. Found: C,76.76; H, 5.61; S,
8.62.
after each cycle. They were given isotropic thermal
parameters 20% higher than those of the carbon to
which they were attached. Least-squares refinements
were carried out by minimizing the function Sw(ꢀFoꢀ−
ꢀFcꢀ)2, where Fo and Fc are the observed and calculated
structure factors, respectively. The weighting scheme
used in the last refinement cycles was w=w%[1−{D F/
6|(Fo)}2]2 where w%=1/S1nArTr(x) with three coeffi-
cients Ar for the Chebyshev polynomial ArTr(x) where
x was Fc/Fc(max) [9]. Models reached convergence
with R=S(ꢀꢀFoꢀ−ꢀFcꢀꢀ)/S(ꢀFoꢀ) and Rw=Sw(ꢀFoꢀ−
ꢀFcꢀ)2/Sw-(Fo)2]1/2, having the values listed in Table 2.
The calculations were carried out with the CRYS-
TALS package programs [10] running on a Pentium II.
The molecular views were realized with the help of
CAMERON [11]. Fractional atomic coordinates, an-
isotropic thermal parameters for non hydrogen atoms
and atomic coordinates for H atoms have been de-
posited at the Cambridge Crystallographic Data
Center.
2,3-Diethyl-4,5-diphenyl-1-phenylphosphole-sulfide
(5b): (52%). Yellow crystals were obtained by diffusion
of pentane into a dichloromethane solution. m.p.=
148–150°C. 31P-NMR (CDCl3): l 54.6. 1H-NMR
(CDCl3): l 0.85 (t, 3H, 3JHH=7.6 Hz, Me) 0.93 (t,
3
3H, JHH=7.6 Hz, Me), 2.43 (m, 2+1H, CH2), 2.61
(m, 1H, CH2), 7.02 (m, 5H, Ph), 7.25–7.51 (m, 8H,
Ph), 7.88 (m, 2H, Ph). 13C-NMR (CDCl3): l 13.60 (d,
3
3JCP=2.1 Hz, CH3), 14.50 (s, CH3), 19.06 (d, JCP
=
13.0 Hz, CH2), 21.16 (d, 2JCP=14.0 Hz, CH2),
1
127.40–135.60 (Ph), 135.90 (d, JCP=76.6 Hz, CꢀEt),
2
137.70 (d, 1JCP=76.8 Hz, CꢀPh), 150.90 (d, JCP
=
2
26.5 Hz, CꢀEt), 151.30 (d, JCP=21.0 Hz, CꢀPh). MS
m/z (rel. int.) 401 (MH+, 100%). Anal. Calc. for
C26H25PS: C, 77.97; H, 6.50; S, 8.00. Found: C,77.51;
H, 6.45; S, 8.12.
2,3-Dipropyl-4,5-diphenyl-1-phenylphosphole-sulfide
(5c): (23%). Yellow crystals were obtained by diffusion
of pentane into a dichloromethane solution. m.p.=
130–132°C. 31P-NMR (CDCl3): l 55.0. 1H-NMR
5. Supplementary material
Tables of anisotropic temperature factors, hydrogen
coordinates and observed and calculated structure fac-
tors are available from the Cambridge Crystallo-
graphic Data Center. Ordering information is given on
any current masthead page.
3
(CDCl3): l 0.74 (t, 3H, JHH=7.4 Hz, Me), 0.80 (t,
3
3H, JHH=7.4 Hz, Me), 1.22 (m, 4H, 2CH2), 2.33 (m,
2+1H, CH2), 2.57 (m, 1H, CH2), 7.00 (m, 5H, Ph),
7.21–7.44 (m, 8H, Ph), 7.91 (m, 2H, Ph).13C-NMR
(CDCl3): l 14.10 (s, CH3), 14.40 (s, CH3), 22.20 (s,
CH2ꢀCH2ꢀCH3), 22.90 (s, CH2ꢀCH2ꢀCH3), 28.30 (d,
2
3JCP=12.3 Hz, CH2ꢀCH2ꢀCH3), 30.00 (d, JCP=13.7
Acknowledgements
Hz, CH2ꢀCH2ꢀCH3), 127.40–132.30 (Ph), 135.65 (d,
1JCP=76.9 Hz, CꢀPr), 137.10 (d, 1JCP=76.6 Hz,
CꢀPh), 150.20 (d, 2JCP=20.2 Hz, CꢀPr), 151.10 (d,
2JCP=26.2 Hz, CꢀPh). MS m/z (rel. int.) 429 (MH+,
We thank the CNRS and Rhoˆne-Poulenc for finan-
cial support, Dr A. Igau for fruitful discussions and
D. Cuny for assistance in synthesis.