ELECTROPHILIC REACTIONS OF ZEROVALENT TUNGSTEN NITRENE AND HYDRAZIDO COMPLEXES WITH PHOSPHINES - SYNTHESIS AND STRUCTURE OF (CO)4W[PPH2CH2PPH2NNME2]

被引：10

作者：

ARNDTSEN, BA

SLEIMAN, HF

MCELWEEWHITE, L

RHEINGOLD, AL

机构：

[1] STANFORD UNIV,DEPT CHEM,STANFORD,CA 94305

[2] UNIV DELAWARE,DEPT CHEM,NEWARK,DE 19716

来源：

ORGANOMETALLICS | 1993年 / 12卷 / 07期

关键词：

D O I：

10.1021/om00031a014

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The low-valent hydrazido complex (CO)5W=NNMe2 (2) reacts with bis(diphenylphosphino)methane (DPPM) to yield the metallacyclic phosphinimine complex (CO)4W[PPh2CH2PPh2NNMe2] (5). Mechanistic studies and extended Huckel molecular orbital calculations suggest that formation of 5 occurs via a highly unusual nucleophilic attack of phosphine at N(alpha) of the hydrazido ligand. Complex 5 has been characterized spectroscopically as well as by X-ray crystallography: P2(1)/n; a = 10.797(3) angstrom, b = 22.761(3) angstrom, c = 12.257(2) angstrom, beta = 90.92(4)degrees, V = 3011.8(11) angstrom3, Z = 4, R(F) = 3.87%, R(wF) = 4.69%, for 4292 reflections, F greater-than-or-equal-to 5.0sigma(F).

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页码：2440 / 2444

页数：5

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