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)

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