Data for: "Halide abstraction competes with oxidative addition in the reactions of aryl halides with [Ni(PMenPh(3-n))4]"

  • Ignacio Funes-Ardoiz (Creator)
  • David Nelson (Creator)
  • Feliu Maseras (Creator)

Dataset

Description

Density functional theory (DFT) calculations have been used to study the oxidative addition of aryl halides to complexes of the type [Ni(PMenPh(3-n))4], revealing the crucial role of an open shell singlet transition state for halide abstraction. The formation of NiI versus NiII has been rationalised through the study of three different pathways: (i) halide abstraction by [Ni(PMenPh(3-n))3], via an open shell singlet transition state; (ii) SN2-type oxidative addition to [Ni(PMenPh(3-n))3], followed by phosphine dissociation; and (iii) oxidative addition to [Ni(PMenPh(3-n))2]. For the case of [Ni(PMe3)4], a microkinetic model was used to show that these data are consistent with the experimentally-observed ratios of NiI and NiII. Importantly, [Ni(PMenPh(3-n))2] complexes often have little if any role in the oxidative addition reaction because they are relatively high in energy. The behaviour of [Ni(PR3)4] complexes in catalysis is therefore likely to differ considerably from those based on diphosphine ligands in which two coordinate Ni0 complexes are the key species undergoing oxidative addition.

A data set collection of computational results is available from the ioChem‐BD repository
Date made available3 Jul 2019

Cite this

Funes-Ardoiz, I. (Creator), Nelson, D. (Creator), Maseras, F. (Creator). (3 Jul 2019). Data for: "Halide abstraction competes with oxidative addition in the reactions of aryl halides with [Ni(PMenPh(3-n))4]"10.19061/iochem-bd-1-55