Expanding the scope of ligand substitution from [M(S2C2Ph2] (M = Ni2+, Pd2+, Pt2+) to afford new heteroleptic dithiolene complexes

Obanda, A., Martinez, K., Schmehl, R. H., Mague, J. T., Rubtsov, I. V., MacMillan, S. N., Lancaster, K. M., Sproules, S. and Donahue, J. P. (2017) Expanding the scope of ligand substitution from [M(S2C2Ph2] (M = Ni2+, Pd2+, Pt2+) to afford new heteroleptic dithiolene complexes. Inorganic Chemistry, 56(17), pp. 10257-10267. (doi:10.1021/acs.inorgchem.7b00971) (PMID:28820242)

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Abstract

The scope of direct substitution of the dithiolene ligand from [M(S2C2Ph2)2] [M = Ni2+ (1), Pd2+ (2), Pt2+ (3)] to produce heteroleptic species [M(S2C2Ph2)2Ln] (n = 1, 2) has been broadened to include isonitriles and dithiooxamides in addition to phosphines and diimines. Collective observations regarding ligands that cleanly produce [M(S2C2Ph2)Ln], do not react at all, or lead to ill-defined decomposition identify soft σ donors as the ligand type capable of dithiolene substitution. Substitution of MeNC from [Ni(S2C2Ph2)(CNMe)2] by L provides access to a variety of heteroleptic dithiolene complexes not accessible from 1. Substitution of a dithiolene ligand from 1 involves net redox disproportionation of the ligands from radical monoanions, –S•SC2Ph2, to enedithiolate and dithione, the latter of which is an enhanced leaving group that is subject to further irreversible reactions.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Sproules, Dr Stephen
Authors: Obanda, A., Martinez, K., Schmehl, R. H., Mague, J. T., Rubtsov, I. V., MacMillan, S. N., Lancaster, K. M., Sproules, S., and Donahue, J. P.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Inorganic Chemistry
Publisher:American Chemical Society
ISSN:0020-1669
ISSN (Online):1520-510X
Published Online:18 August 2017
Copyright Holders:Copyright © 2017 The American Chemical Society
First Published:First published in Inorganic Chemistry 56(17):10257–10267
Publisher Policy:Reproduced in accordance with the copyright policy of the publisher

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