Issue 12, 2013

Accelerating Ni(ii) precatalyst initiation using reactive ligands and its impact on chain-growth polymerizations

Abstract

Nickel(II) complexes with varying reactive ligands, which were designed to selectively accelerate the initiation rate without influencing the propagation rate in the chain-growth polymerization of π-conjugated monomers, were investigated. Precatalysts with electronically varied reacting groups led to faster initiation rates and narrower molecular weight distributions. Computational studies revealed that the reductive elimination rates are largely modulated by the ability of the two reacting arenes to stabilize the increasing electron density on the catalyst during reductive elimination. Overall, these studies provide insight into a key mechanistic step of cross-coupling reactions (reductive elimination) and highlight the importance of initiation in controlled chain-growth polymerizations.

Graphical abstract: Accelerating Ni(ii) precatalyst initiation using reactive ligands and its impact on chain-growth polymerizations

Supplementary files

Additions and corrections

Article information

Article type
Paper
Submitted
15 Nov 2012
Accepted
12 Dec 2012
First published
02 Jan 2013

Dalton Trans., 2013,42, 4218-4222

Accelerating Ni(II) precatalyst initiation using reactive ligands and its impact on chain-growth polymerizations

S. R. Lee, J. W. G. Bloom, S. E. Wheeler and A. J. McNeil, Dalton Trans., 2013, 42, 4218 DOI: 10.1039/C2DT32735J

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