X-ray crystal structures of Cp*Ni(PEt3)X [X=Br, O(p-C6H4Me), NH(p-C6H4Me), S(p-C6H4Me), OCH3, CH2C6H5, Me, H, PEt3+].: Understanding distortions and transinfluences in cyclopentadienyl complexes

被引:62
作者
Holland, PL [1 ]
Smith, ME [1 ]
Andersen, RA [1 ]
Bergman, RG [1 ]
机构
[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA
关键词
D O I
10.1021/ja971830o
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The syntheses of Cp*Ni(PEt3)Me and Cp*Ni(PEt3)Br have been accomplished, starting from the useful starting material Cp*Ni(PEt3)(acac). The X-ray crystal structures of Cp*Ni(PEt3)X (X = Br, O(p-C6H4Me), NH(p-C6H4Me), S(p-C6H4Me), OCH3, Me, CH2Ph, H, PEt3+) have been determined, providing a large sample of similar structures for the analysis of ring distortions as well as a systematic variation of X in order to evaluate the trans influence felt by opposite sides of the cyclopentadienyl ring. Major advances include demonstration that Cp can reduce its electron donation to a metal without "slipping", the rational analysis of cyclopentadienyl distortions, and a well-supported trans-influence series for cyclopentadienylmetal complexes. In sum, d(8) Cp*NiL2 complexes are similar to d(8) NiL4 square-planar complexes in terms of bond lengths, binding geometry, and trans influences.
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页码:12815 / 12823
页数:9
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