V.I. Sokolo6 et al. / Journal of Organometallic Chemistry 582 (1999) 246–251
251
and the yellow precipitate was collected, giving 0.3995 g
(95%) of 5, [h]D +85.5° (CH2Cl2, c 0.5), m.p. 112°C.
Found: C, 55.05; H, 6.40; P, 6.18. C44H62O8P2PdCl2
C(21%) 1.430(1), O(3)–C(21A) 1.430(1), C(21)–C(22)
1.52(1), C(21A)–C22(A) 1.52(1), O(2)–P(1) 1.580(5),
O(2%)–P(1%) 1.580(5), O(3)–P(1) 1.580(5), and O(3%)–
1
,
Calc.: C, 55.4; H, 6.52; P, 6.47%. H-NMR (CD2Cl2,
P(1%) 1.580(5) A. Full-matrix least-squares refinement
ppm): 0.8 (s, 3H, CH3), 1.0–2.75 (m, 21H, alk. H), 4.16
(q, 4H, (CH3CH2O)2P), 6.81–7.16 (m, 3H, C6H3). 31P-
NMR (CD2Cl2, ppm): 89.71.
against F2 (528 parameters) in an anisotropic approxi-
mation using 5849 reflections was carried, resulting in
R1=0.057 (for 3708 reflections with F\4(F)), wR2=
0.149, and S=0.91. The final atomic coordinates are
given in Table 1. Selected bond lengths and angles are
listed in Tables 2 and 3.
4.6. 1-Palladiochloride[O-diethoxyphosphino-(+)-
estrone] dimer (6a) and 3-palladio-chloride[O-dieth-
oxyphosphino-(+)-estrone] dimer (6b)
To 0.3404 g (0.36 mM) of 5 ([h]D +85.5°) suspended
in toluene (25 ml) 0.075 g (0.42 mM) of PdCl2 was
added, and the mixture was heated under argon on an
oil bath for 12 h. Progress of the reaction was moni-
tored by the presence of HCl in outgoing gases. After
cooling, the reaction mixture was filtered and evapo-
rated to dryness. After crystallization of 6a and 6b
(total yield 90%) from the mixture in CH2Cl2:heptane,
6b was obtained in pure form. [h]D +150.4° (CH2Cl2,
c 0.85), m.p. 185°C (dec.). Found: C, 49.60; H, 5.68; P,
5.81. C22H30O4PPdCl Calc.: C, 49.73; H, 5.69; P, 5.83%.
Acknowledgements
This work had been carried out with the financial
support from the Russian Foundation for Basic Re-
search (RFBR), Project Nos. 96-03-33446, 97-03-
33783a and 96-15-97367.
References
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1
1H-NMR (CDCl3, ppm): H-NMR (CDCl3, ppm): 0.84
(s, 3H, CH3), 1.2–2.8 (m, 21H, alk. H), 4.2–4.6 (q, 4H,
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4.7. X-ray structural in6estigation of 6b
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3
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,
and c=34.34(1) A, V=4605(2) A , space group
P212121, Z=4, Dcalc. =1.533 g cm−3, crystal size 0.5×
0.4×0.3 mm, v=1.016 mm−1, F(000)=2176.
The intensity of 5911 independent reflections was
measured on an automatic four-circle Siemens P3/PC
diffractometer (graphite monochromated Mo–Ka radi-
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The structure was solved by direct methods using the
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relevant H-atom (where n=1.5 for methyl groups and
n=1.2 for other hydrogen atoms). Eleven restraints
were used during refinement: O(1)–C(3) 1.430(1),
O(2%)–C(19%) 1.430(1), O(3)–C(21) 1.430(1), O(3%)–
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.