Abstract
Oxo-centered trinuclear transition metal clusters have potential applications in catalysis and biomedical research. Although, the synthesis and catalytic properties of these compounds have been studied extensively, little is known regarding their basic fundamental chemistry. Research focusing on the reactivity of cluster compounds and its dependence on structure is important as it will aid in the development of transition metal cluster-based catalysts. In this study, the reactivity of coordinated water ligands for a series of bioxo-capped trinuclear molybdenum clusters with bridging carboxylate ligands was examined in detail. This work utilized variable temperature 1H NMR to determine rate constants and activation parameters for the first water substitution step. Rates of water substitution were roughly correlated to metal-water bond lengths and calculated activation parameters were used to assign an associative or dissociative reaction mechanism. A newly synthesized cluster with bridging chloroacetate ligands was also characterized and a new alkylidyne-capped cluster was discovered.