Direct observation of β-chloride elimination from an isolable β-chloroalkyl complex of square-planar nickel

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

doi:10.1021/ja508956q

Direct observation of β-chloride elimination from an isolable β-chloroalkyl complex of square-planar nickel

J Am Chem Soc. 2014 Nov 5;136(44):15481-4. doi: 10.1021/ja508956q. Epub 2014 Oct 21.

Authors

Alex E Carpenter¹, Andrew J McNeece, Brandon R Barnett, Alexander L Estrada, Charles C Mokhtarzadeh, Curtis E Moore, Arnold L Rheingold, Charles L Perrin, Joshua S Figueroa

Affiliation

¹ Department of Chemistry and Biochemistry, University of California, San Diego , 9500 Gilman Drive, Mail Code 0358, La Jolla, California 92093-0358, United States.

PMID: 25317481
DOI: 10.1021/ja508956q

Abstract

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 β-chloroalkyl in a system relevant to coordination-insertion polymerization of polar olefins. Kinetic analysis of NiCl(CCl2CCl3)(CNAr(Mes2))2 decomposition indicates that β-chloride (β-Cl) elimination proceeds by a unimolecular mechanism that does not require initial dissociation of a CNAr(Mes2) ligand. The results suggest that a direct β-Cl elimination pathway is available to four-coordinate, Group 10 metal vinyl chloride polymerization systems.