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,* and Robert H. Crabtree*
Department of Chemistry, Yale University, 225 Prospect Street, New Haven, Connecticut 06520, United States
DOI: 10.1021/jacs.5b12148
ABSTRACT
We describe facial and meridional isomers of [RhIII(pyalk)3], as well as meridional [RhIV(pyalk)3]+
{pyalk =2-(2-pyridyl)-2-propanoate}, the first coordination complex in an N,O-donor environment to show a clean, reversible RhIII/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.
{pyalk =2-(2-pyridyl)-2-propanoate}, the first coordination complex in an N,O-donor environment to show a clean, reversible RhIII/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.
コメント