A comparative study of amino phenoxide zirconium catalysts {in the|within the|inside the} hydrophosphination of alkenes with diphenylphosphine reveals enhanced activity upon irradiation. The origin of {improved|enhanced} reactivity is hypothesized to {result|outcome} from substrate insertion upon an n to d charge transfer of a Zr–P bond {in the|within the|inside the} excited state of putative phosphido (Zr–PR2) intermediates. TD-DFT {analysis|evaluation} reveals the lowest lying excited state {in the|within the|inside the} proposed active catalysts are dominated by a P 3p to Zr 4d MLCT, presumably {leading|top|major} to enhanced catalysis. This hypothesis follows from triamidoamine-supported zirconium catalysts but demonstrates the generality of photocatalytic hydrophosphination with d0 metals. 2-(Aminooxy)ethanamine dihydrochloride web Buy4-(Dimethylamino)but-2-ynoic acid PMID:23381626
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