title: Direct observation of β-chloride elimination from an isolable β-chloroalkyl complex of square-planar nickel.
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.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego , 9500 Gilman Drive, Mail Code 0358, La Jolla, California 92093-0358, United States.
authors.forename: Alex E
authors.initials: AE
authors.lastname: Carpenter
authors.forename: Andrew J
authors.initials: AJ
authors.lastname: McNeece
authors.forename: Brandon R
authors.initials: BR
authors.lastname: Barnett
authors.forename: Alexander L
authors.initials: AL
authors.lastname: Estrada
authors.forename: Charles C
authors.initials: CC
authors.lastname: Mokhtarzadeh
authors.forename: Curtis E
authors.initials: CE
authors.lastname: Moore
authors.forename: Arnold L
authors.initials: AL
authors.lastname: Rheingold
authors.forename: Charles L
authors.initials: CL
authors.lastname: Perrin
authors.forename: Joshua S
authors.initials: JS
authors.lastname: Figueroa