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Mo(NMe2)4 and the tridentate, dipyrrolyl ligand H2dpmames were found to form 5-coordinate Mo(NMe2)2(dpmames) (1), which exhibits spin-crossover behaviour in solution. The complex is a ground state singlet with a barrier of 1150 cm−1 for production of the triplet in d8-toluene. The complex reacts with 1,1-disubstituted hydrazines or O-benzylhydroxylamine to produce nitrido MoN(NMe2)(dpmames). The mechanism of the 1,1-dimethylhydrazine reaction with 1 was examined along with the mechanism of substitution of NMe2 with H2NNMe2 in a diamagnetic zirconium analogue. The proposed mechanism involves production of a hydrazido(1–) intermediate, Mo(NMe2)(NHNMe2)(dpmames), which undergoes an α,β-proton shift and N–N bond cleavage with metal oxidation to form the nitrido. The rate law for the reaction was found to be −d/dt = kobs[hydrazine] by initial rate experiments and examination of the full reaction profile. This conversion from hydrazido(1–) to nitrido is somewhat analogous to the proposed mechanism for O–O bond cleavage in some peroxidases.
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