Light-Driven Hydrogen Production from Aqueous Protons using Molybdenum Catalysts
- 27 August 2014
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 53 (18), 9860-9869
- https://doi.org/10.1021/ic501440a
Abstract
Homogeneous light-driven systems employing molecular molybdenum catalysts for hydrogen production are described. The specific Mo complexes studied are six-coordinate bis(benzenedithiolate) derivatives having two additional isocyanide or phosphine ligands to complete the coordination sphere. Each of the complexes possesses a trigonal prismatic coordination geometry. The complexes were investigated as proton reduction catalysts in the presence of [Ru(bpy)3](2+), ascorbic acid, and visible light. Over 500 TON are obtained over 24 h. Electrocatalysis occurs between the Mo(IV)/Mo(III) and Mo(III)/Mo(II) redox couples, around 1.0 V vs SCE. Mechanistic studies by (1)H NMR spectroscopy show that upon two-electron reduction the Mo(CNR)2(bdt)2 complex dissociates the isocyanide ligands, followed by addition of acid to result in the formation of molecular hydrogen and the Mo(bdt)2 complex.Funding Information
- Division of Chemistry (CHE-1137057, CHE-1151789)
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