W.-C. Chiang et al. / Inorganica Chimica Acta 334 (2002) 213Á
/218
217
4.2.2. Pt(PPh3)2[h3-CH2C(OPO3H)CH2] (5)
To two-neck round-bottom flask containing
radiation. The cell parameters were determined by a
least-squares fit on 25 reflections. Intensity data were
corrected for absorption on the basis of an experimental
c rotation curve. The refinement procedure was done
by a full-matrix least-squares method including all the
non-hydrogenic atoms anisotropically. Hydrogen atoms
a
[nBu4N](H2PO4) (80 mg, 0.237 mmol), pre-dried di-
chloromethane (5 ml) was transferred in vacuo. A
dichloromethane (25 ml) solution of 1 (200 mg, 0.237
mmol) was placed in an addition funnel and added to
the flask slowly. The reaction was allowed to last at
0 8C for 1 h, and then concentrated. A yellow solid was
precipitated by adding diethyl ether. Washing with
Ethanol gave mixed products (170 mg) of 5 and 6 in
were fixed at the ideal geometry and the CÃ
/
H distance
˚
of 1.0 A; their isotopic thermal parameters were fixed to
the values of the attached carbon atoms at the conver-
gence of the isotropic refinement. Atomic scattering
factors were taken from the International Tables of
Crystallographic Data, Vol. IV [13]. Computing pro-
grams are from the NRC VAX package [14]. Crystal-
lographic data and selected atomic coordinates
4.8:5.2 relative yields. Separation was not successful. 31
NMR (CDCl3, 121.49 MHz) d ꢁ1.88 (JPÃPt 19.6 Hz),
3694 Hz); H NMR (CDCl3, 300 MHz) d
2.43 (2H, dd with 195Pt satellites, JHÃH
2.8 Hz, JHÃP
8.8 Hz, JHÃPt 47.6 Hz, Hanti), 3.79 (2H, d, JHÃH 2.8
P
/
ꢃ
/
1
18.1 (JPÃPt
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
and bond parameters are collected in Tables IIIÁIX.
/
Hz, Hsyn), 6.8Á
/
7.8 (30H, m, phenyl H), 9.42 (br, OH);
The rest of data is supplied in the supplementary
material.
MS (FAB, m/z): 856.1 (Mꢀ).
4.2.3. {Pt2(PPh3)4[m-h6-(C2H4C)2(PO4)]}(BF4) (6)
In
a
round-bottom flask, was placed trans-
5. Supplementary material
Pt(PPh3)2(C3H3)Cl (280 mg, 0.35 mmol) and equimolar
amounts of AgBF4. Dichloromethane (15 ml) was
introduced under vacuo. The solution was allowed to
Detailed crystal data, atomic coordinates, bond
parameters, anisotropic parameters, and structure fac-
tors are available from G.-H. Lee or J.-T. Chen upon
request.
react at ꢁ20 8C for 20 min. When AgBr was removed
/
by filtration, [nBu4N](H2PO4) (52 mg, 0.177 mmol) was
added and the reaction solution was stirred at 0 8C for 1
h. A yellow solid mixture was precipitated from ethanol/
diethyl ether (1:4) in 87% yield (260 mg). Trace of
[nBu4N](BF4) was remained to cause the failure of
elemental analysis and growth for single crystals. 31P
Acknowledgements
We thank the National Science Council, Taiwan,
ROC for the financial support.
NMR (CDCl3, 81.015 MHz) d ꢁ
17.47 (JPÃPt
3779 Hz); 1H NMR (CDCl3, 200 MHz) d
2.53 (2H, dd with 195Pt satellites, JHÃH
3.4 Hz, JHÃP
8.7 Hz, JHÃPt 40.5 Hz, Hanti), 3.72 (2H, d, JHÃH 3.4
Hz, Hsyn), 6.8Á
7.8 (30H, m, phenyl H); 13C NMR
(CDCl3, 75.469 MHz) d 57.6 (dd with 195Pt satellites,
JCÃP 3.9, 33.8 Hz, JCÃPt 91.1 Hz, Ct), 127Á135
2.8 Hz, Cc); MS (FAB, m/
/
14.39 (JPÃPt
ꢃ
/
22 Hz),
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
/
References
[1] (a) A. Wojcicki, New J. Chem. 18 (1994) 61;
(b) A. Wojcicki, New J. Chem. 21 (1997) 733.
ꢃ
/
ꢃ
/
/
(phenyl C), 148.2 (t, JCÃP
ꢃ
/
[2] J.-T. Chen, Coord. Chem. Rev. 190Á192 (1999) 1143.
/
z): 1614.5 (Mꢀ).
[3] (a) V.V. Krivykh, E.S. Taits, P.V. Petrovskii, Y.T. Struchkov,
A.I. Yanovskii, Mendeleev Commun. (1991) 103;
(b) T.-M. Huang, R.-H. Hsu, C.-S. Yang, J.-T. Chen, G.-H. Lee,
Y. Wang, Organometallics 13 (1994) 3657.
4.2.4. [Pt2(PPh3)4(m4-PO4)](BF4) (7)
A CDCl3 solutions containing 30 mg of 6 was left in
atmosphere at 50 8C. The formation of complex 7 that
accounted for 60% of starting 6 was obtained after 24 h
based on the 31P NMR integration, along with the
quantitative formation of acetone which was confirmed
by coinjection with authentic sample. Recrystallization
[4] F.-Y. Tsai, H.-W. Chen, J.-T. Chen, G.-H. Lee, Y. Wang,
Organometallics 16 (1997) 822.
[5] H. Kurosawa, Chem. Lett. 223 (1997) 1.
[6] (a) T.-M. Huang, R.-S. Hsu, C.-S. Yang, J.-T. Chen, G.-H. Lee,
Y. Wang, Organometallics 13 (1994) 3657;
(b) M.W. Baize, J.L. Furilla, A. Wojcicki, Inorg. Chim. Acta 223
(1994) 1.
of 7 in CHCl3Á
crystals suitable for X-ray analysis. 31P NMR (CDCl3,
121.5 Hz) d 7.21 (d, JPÃPt 3966 Hz, JPÃP 6.1 Hz),
52.18 (m, JPÃPt 125.1 Hz, JPÃP 6.1 Hz).
/
THFÁ
/
cyclohexane resulted in the single
[7] (a) M.W. Baize, P.W. Blosser, V. Plantevin, D.G. Schimpff, J.C.
Gallucci, A. Wojcicki, Organometallics 15 (1996) 164;
(b) T.-M. Huang, R.-S. Hsu, C.-S. Yang, J.-T. Chen, G.-H. Lee,
Y. Wang, Organometallics 13 (1994) 3657;
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
(c) A. Ohsuka, T. Fujimori, T. Hirao, H. Kurosawa, I. Ikeda, J.
Chem. Soc., Chem. Commun. (1993) 1039;
4.3. X-ray crystallographic analysis
(d) F.-Y. Tsai, R.-H. Hsu, T.-M. Huang, J.-T. Chen, G.-H. Lee,
Y. Wang, J. Organomet. Chem. 520 (1996) 85.
Diffraction data were measured on a Nonius CAD-4
diffractometer with graphite-monochromatized Mo Ka
[8] V. Plantevin, P.W. Blosser, J.C. Gallucci, A. Wojcicki, Organo-
metallics 13 (1994) 3651.
Chiang, Wen-Chi
