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

Antony Obanda; Kristina Martinez; Russell H Schmehl; Joel T Mague; Igor V Rubtsov; Samantha N MacMillan; Kyle M Lancaster; Stephen Sproules; James P Donahue

doi:10.1021/acs.inorgchem.7b00971

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

Inorg Chem. 2017 Sep 5;56(17):10257-10267. doi: 10.1021/acs.inorgchem.7b00971. Epub 2017 Aug 18.

Authors

Antony Obanda¹, Kristina Martinez¹, Russell H Schmehl¹, Joel T Mague¹, Igor V Rubtsov¹, Samantha N MacMillan², Kyle M Lancaster², Stephen Sproules³, James P Donahue¹

Affiliations

¹ Department of Chemistry, Tulane University , 6400 Freret Street, New Orleans, Louisiana 70118, United States.
² Department of Chemistry and Chemical Biology, Cornell University , 162 Sciences Drive, Ithaca, New York 14853, United States.
³ School of Chemistry, University of Glasgow , University Avenue, Glasgow, Lanarkshire G12 8QQ, United Kingdom.

PMID: 28820242
DOI: 10.1021/acs.inorgchem.7b00971

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)₂L_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(S₂C₂Ph₂)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(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.