SYNTHESIS AND P-31 NMR-STUDIES OF UNSYMMETRICAL CIS-DIPHOSPHINOALKENES AND THEIR COMPLEXES WITH NICKEL(II), PALLADIUM(II), AND PLATINUM(II)

被引:73
作者
CARTY, AJ
JOHNSON, DK
JACOBSON, SE
机构
[1] Waterloo Campus, Department of Chemistry, University of Waterloo, Ontario, Canada, Waterloo
关键词
D O I
10.1021/ja00513a027
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Bis(phosphinoalkyne) complexes m-Cl2M(Ph2PC≡CR)2 (M = Pd, Pt; R = CF3, Ph, t-Bu) undergo a facile 1:1 reaction with secondary phosphines HPR'R˝ (R'R˝ = Ph, C2H4CN; R’ = Et, R˝ = Ph) to give stereospecifically the cis, 2-cis-phosphinoalk-1-ene complexes cis-Cl2M(Ph2PCH=C(R)PR'R˝). The uncoordinated diphosphinoalk-1-enes may be obtained by treatment of the corresponding Pt(II) complex with excess cyanide ion. Complexes cis-Cl2Ni(Ph2PCH==C(R)-PR'R˝) are obtained by reaction of cis-Ph2PCH=C(R)PR'R˝ with anhydrous nickel(II) chloride. The free diphosphinoalk-lenes and their Ni(II), Pd(II), and Pt(II) complexes are characterized by elemental analysis, mass spectrometry, IR, 1H NMR, and 31P NMR spectroscopy. Factors affecting 31P chemical shifts, coordination chemical shifts, and P-P couplings in these systems are discussed. © 1979, American Chemical Society. All rights reserved.
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页码:5612 / 5619
页数:8
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