A series of bis(phosphine) molybdenum(ii) diazenides [(dppe)Mo(NNCy)(I)], [(dppe)(CHCN)Mo(NNCy)][BArF] and [(dppe))(3,5-(CF)CHCN)Mo(NNCy)][BArF] (dppe = 1,2-bis(diphenylphosphino)ethane; Cy = cyclohexyl; ArF = (3,5-(CF)CH)) were synthesized and structurally characterized. Treatment of the diazenido complexes with a stoichiometric amount of [H(OEt)][BArF] afforded the corresponding molybdenum(iv) hydrazido species [(dppe)Mo(NNHCy)(I)][BArF], [(dppe)(CHCN)Mo(NNHCy)][BArF] and [(dppe)(3,5-(CF)CHCN)Mo(NNHCy)][BArF], enabling the study of N-H bond dissociation free energies (BDFEs) in the classical Chatt-type bis(phosphine) diazenide platform as a function of ligand (L) trans to the nitrogenous fragment. Deprotonation and electrochemical experiments established that the trans nitrile 3,5-(CF)CHCN afforded the least reducing molybdenum(iv) hydrazido complex in the series ( = -1.32 V vs. Fc/Fc) with the most acidic N-H bond (pK < 2.6, THF), whereas the ligands CHCN ( = -1.60 V, pK < 5.5) and I ( = -2.03 V, pK = 9.3) gave more reducing complexes with less acidic N-H bonds. Computational (DFT) studies confirm weak N-H bond strengths of 32.8 (L = I), 35.4 (L = CHCN) and 36.2 kcal mol (L = 3,5-(CF)CHCN) in the hydrazido series.
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