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• 作者：Patrick L. Holland ; Michael E. Smith ; Richard A. Andersen ; and Robert G. Bergman
• 刊名：Journal of the American Chemical Society
• 出版年：1997
• 出版时间：December 31, 1997
• 年：1997
• 卷：119
• 期：52
• 页码：12815 - 12823
• 全文大小：228K
• 年卷期：v.119,no.52(December 31, 1997)
• ISSN：1520-5126

文摘

The syntheses of Cp*Ni(PEt₃)Me andCp*Ni(PEt₃)Br have been accomplished, startingfrom the usefulstarting material Cp*Ni(PEt₃)(acac). TheX-ray crystal structures of Cp*Ni(PEt₃)X (X = Br,O(p-C₆H₄Me),NH(p-C₆H₄Me),S(p-C₆H₄Me), OCH₃,Me, CH₂Ph, H, PEt₃⁺) havebeen determined, providing a large sample of similarstructures for the analysis of ring distortions as well as a systematicvariation of X in order to evaluate the transinfluence felt by opposite sides of the cyclopentadienyl ring.Major advances include demonstration that Cp canreduce its electron donation to a metal without"slipping", the rational analysis of cyclopentadienyl distortions,anda well-supported trans-influence series for cyclopentadienylmetalcomplexes. In sum, d⁸ Cp*NiL₂ complexesaresimilar to d⁸ NiL₄ square-planar complexes interms of bond lengths, binding geometry, and transinfluences.