Direct Observation of 尾-Chloride Elimination from an Isolable 尾-Chloroalkyl Complex of Square-Planar Nickel

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• 作者：Alex E. Carpenter ; Andrew J. McNeece ; Brandon R. Barnett ; Alexander L. Estrada ; Charles C. Mokhtarzadeh ; Curtis E. Moore ; Arnold L. Rheingold ; Charles L. Perrin ; Joshua S. Figueroa
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：November 5, 2014
• 年：2014
• 卷：136
• 期：44
• 页码：15481-15484
• 全文大小：315K
• ISSN：1520-5126

文摘

Reported here are the isolation, structural characterization, and decomposition kinetics of the four-coordinate pentachloroethyl nickel complex, NiCl(CCl₂CCl₃)(CNAr^Mes2)₂ (Ar^Mes2 = 2,6-(2,4,6-Me₃C₆H₂)₂C₆H₃). This complex is a unique example of a kinetically persistent 尾-chloroalkyl in a system relevant to coordination鈥搃nsertion polymerization of polar olefins. Kinetic analysis of NiCl(CCl₂CCl₃)(CNAr^Mes2)₂ decomposition indicates that 尾-chloride (尾-Cl) elimination proceeds by a unimolecular mechanism that does not require initial dissociation of a CNAr^Mes2 ligand. The results suggest that a direct 尾-Cl elimination pathway is available to four-coordinate, Group 10 metal vinyl chloride polymerization systems.