Reduction pathway of end-on terminally coordinated dinitrogen. V. N-N bond cleavage in Mo/W hydrazidium complexes with diphosphine coligands. Comparison with triamidoamine systems

N-N cleavage of the dialkylhydrazido complex [W(dppe)2(NNC5H10)] (B(W)) upon treatment with acid, leading to the nitrido/imido complex and piperidine, is investigated experimentally and theoretically. In acetonitrile and at room temperature, B(W) reacts orders of magnitude more rapidly with HNEt3BPh4 than its Mo analogue, [Mo(dppe)2(NNC5H10)] (B(Mo)). A stopped-flow experiment performed for the reaction of B(W) with HNEt3BPh4 in propionitrile at -70 degrees C indicates that protonation of B(W) is completed within the dead time of the stopped-flow apparatus, leading to the primary protonated intermediate B(W)H+. Propionitrile coordination to this species proceeds with a rate constant k(obs(1)) of 1.5 +/- 0.4 s(-1), generating intermediate RCN-B(W)H+ (R = Et) that rapidly adds a further proton at Nbeta and then mediates N-N bond splitting in a slower reaction (k(obs(2)) = 0.35 +/- 0.08 s(-1), 6 equiv of acid). k(obs(1)) and k(obs(2)) are found to be independent of the acid concentration. The experimentally observed reactivities of B(Mo) or B(W) with acids in nitrile solvents are reproduced by DFT calculations. In particular, geometry optimization of models of solvent-coordinated, Nbeta-protonated intermediates is found to lead spontaneously to separation into the nitrido/imido complexes and piperidine/piperidinium, corresponding to activationless heterolytic N-N bond cleavage processes. Moreover, DFT indicates a spontaneous cleavage of nonsolvated B(W) protonated at Nbeta. In the second part of this article, a theoretical analysis of the N-N cleavage reaction in the Mo(III) triamidoamine complex [HIPTN3N]Mo(N2) is presented (HIPTN3N = hexaisopropylterphenyltriamidoamine). To this end, DFT calculations of the Mo(III)N2)triamidoamine complex and its protonated and reduced derivatives are performed. Calculated structural and spectroscopic parameters are compared to available experimental data. N-N cleavage most likely proceeds by one-electron reduction of the Mo(V) hydrazidium intermediate [HIPTN3N]Mo(NNH3)+, which is predicted to have an extremely elongated N-N bond. From an electronic-structure point of view, this reaction is analogous to that of Mo/W hydrazidium complexes with diphos coligands. The general implications of these results with respect to synthetic N2 fixation are discussed.