Understanding the Radical Nature of an Oxidized Ruthenium Tris(thiolate) Complex and Its Role in the Chemistry

Hao Tang; Jia Guan; Michael B Hall

doi:10.1021/jacs.5b09309

Understanding the Radical Nature of an Oxidized Ruthenium Tris(thiolate) Complex and Its Role in the Chemistry

J Am Chem Soc. 2015 Dec 23;137(50):15616-9. doi: 10.1021/jacs.5b09309. Epub 2015 Dec 14.

Authors

Hao Tang¹, Jia Guan¹, Michael B Hall¹

Affiliation

¹ Department of Chemistry, Texas A&M University , College Station, Texas 77845, United States.

PMID: 26592259
DOI: 10.1021/jacs.5b09309

Abstract

The spectroscopically observable tris(thiolate) complex [Ru(dppbt)3](+) (1(+)) (dppbt = diphenylphosphinobenzenethiolate) is reported to have chemistry based on thiyl-radical character. High-level ab initio methods predict the ground-state electronic structure of 1(+) to be an open-shell diradical singlet state with antiferromagnetic coupling between (S = 1/2) Ru(III) and (S = 1/2) S pz, rather the previous description based on a diradical state involving two S p orbitals. These new results provide an improved understanding of the experimental chemistry of 1(+) and related species.

Publication types

Research Support, Non-U.S. Gov't