Two new hybrid molybdenum(IV) Mo3 S7 cluster complexes derivatized with diimino ligands have been prepared by replacement of the two bromine atoms of [Mo3 S7 Br6 ](2-) by a substituted bipyridine ligand to afford heteroleptic molybdenum(IV) Mo3 S7 Br4 (diimino) complexes. Adsorption of the Mo3 S7 cores from sample solutions on TiO2 was only achieved from the diimino functionalized clusters. The adsorbed Mo3 S7 units were reduced on the TiO2 surface to generate an electrocatalyst that reduces the overpotential for the H2 evolution reaction by approximately 0.3 V (for 1 mA cm(-2) ) with a turnover frequency as high as 1.4 s(-1) . The nature of the actual active molybdenum sulfide species has been investigated by X-ray photoelectron spectroscopy. In agreement with the electrochemical results, the modified TiO2 nanoparticles show a high photocatalytic activity for H2 production in the presence of Na2 S/Na2 SO3 as a sacrificial electron donor system.
Keywords: cluster compounds; electrochemistry; hydrogen; molybdenum; water splitting.
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