Halide Abstraction Competes with Oxidative Addition in the Reactions of Aryl Halides with [Ni(PMe_n Ph_(3-n) )₄ ].

ABSTRACT: Density functional theory (DFT) calculations have been used to study the oxidative addition of aryl halides to complexes of the type [Ni(PMe_n Ph_(3-n) )₄ ], revealing the crucial role of an open-shell singlet transition state for halide abstraction. The formation of Ni^I versus Ni^II has been rationalised through the study of three different pathways: (i) halide abstraction by [Ni(PMe_n Ph_(3-n) )₃ ], via an open-shell singlet transition state; (ii) S_N 2-type oxidative addition to [Ni(PMe_n Ph_(3-n) )₃ ], followed by phosphine dissociation; and (iii) oxidative addition to [Ni(PMe_n Ph_(3-n) )₂ ]. For the overall reaction between [Ni(PMe

SUBMITTER: Funes-Ardoiz I 

PROVIDER: S-EPMC5725734 | biostudies-literature | 2017 Nov

REPOSITORIES: biostudies-literature