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Updated: Mar 10, 2026

Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction
Published on: August 23, 2018
Solvent-Dependent Thermochemistry of an Iridium/Ruthenium H2 Evolution Catalyst
Kelsey R Brereton1, Catherine L Pitman1, Thomas R Cundari2
1Department of Chemistry, University of North Carolina at Chapel Hill , Chapel Hill, North Carolina 27599-3290, United States.
Abstract:
The hydricity of the heterobimetallic iridium/ruthenium catalyst [Cp*Ir(H)(μ-bpm)Ru(bpy)2]3+ (1, where Cp* = η5-pentamethylcyclopentadienyl, bpm = 2,2'-bipyrimidine, and bpy = 2,2'-bipyridine) has been determined in both acetonitrile (63.1 kcal mol-1) and water (29.7 kcal mol-1). Hydride 1 features a large increase in the hydride donor ability when the solvent is changed from acetonitrile to water. The acidity of 1, in contrast, is essentially solvent-independent because 1 remains strongly acidic in both solvents. On the basis of an X-ray crystallographic study, spectroscopic analysis, and time-dependent density functional theory calculations, the disparate reactivity trends are ascribed to substantial delocalization of the electron density onto both the bpm and bpy ligands in the conjugate base of 1, [Cp*Ir(μ-bpm)Ru(bpy)2]2+ (3). The H2 evolution tendencies of 1 are considered in the context of thermodynamic parameters.
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