On carboxylate as a leaving group at the active site of Mo nitrogenase: electrochemical reactions of some MO and W carboxylates, formation of mono-, di- and tri-hydrides and the detection of an MoH 2(N 2) intermediate

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A carboxylate ligand can function as a leaving group at a reduced molybdenum dihydride centre and this exposes a site at which dinitrogen or other small molecules can bind ; dihydrogen loss occurs after substrate binding ; protic attack intercepts carboxylate loss affording a trihydride intermediate which can partake in a hydrogen evolution cycle : it is suggested that carboxylate loss from the reduced Mo centre of nitrogenase might similarly lead to substrate binding and thence obligatory evolution of H 2.