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The scope of direct substitution of the dithiolene ligand from [M(S 2 C 2 Ph 2 ) 2 ] [M = Ni 2+ (1), Pd 2+ (2), P 2+ (3)] to produce heteroleptic species [M(S 2 C 2 Ph 2 ) 2 L n ] (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(S 2 C 2 Ph 2 )L n ], 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(S 2 C 2 Ph 2 )(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 • SC 2 Ph 2 , to enedithiolate and dithione, the latter of which is an enhanced leaving group that is subject to further irreversible reactions.

inorganic chemistry

Expanding the Scope of Ligand Substitution from [M(S2C2Ph2] (M = Ni2+, Pd2+, Pt2+) To Afford New Heteroleptic Dithiolene Complexes