A Stable Coordination Complex of Rh(IV) in an N,O-Donor Environment

Shashi B Sinha; Dimitar Y Shopov; Liam S Sharninghausen; David J Vinyard; Brandon Q Mercado; Gary W Brudvig; Robert H Crabtree

doi:10.1021/jacs.5b12148

A Stable Coordination Complex of Rh(IV) in an N,O-Donor Environment

J Am Chem Soc. 2015 Dec 23;137(50):15692-5. doi: 10.1021/jacs.5b12148. Epub 2015 Dec 10.

Authors

Shashi B Sinha¹, Dimitar Y Shopov¹, Liam S Sharninghausen¹, David J Vinyard¹, Brandon Q Mercado¹, Gary W Brudvig¹, Robert H Crabtree¹

Affiliation

¹ Department of Chemistry, Yale University , 225 Prospect Street, New Haven, Connecticut 06520, United States.

PMID: 26641941
DOI: 10.1021/jacs.5b12148

Abstract

We describe facial and meridional isomers of [Rh(III)(pyalk)3], as well as meridional [Rh(IV)(pyalk)3](+) {pyalk =2-(2-pyridyl)-2-propanoate}, the first coordination complex in an N,O-donor environment to show a clean, reversible Rh(III/IV) redox couple and to have a stable Rh(IV) form, which we characterize by EPR and UV-visible spectroscopy as well as X-ray crystallography. The unprecedented stability of the Rh(IV) species is ascribed to the exceptional donor strength of the ligands, their oxidation resistance, and the meridional coordination geometry.

Publication types

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