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N–N Bond Cleavage of Mid-Valent Ta(IV) Hydrazido and Hydrazidium Complexes Relevant to the Schrock Cycle for Dinitrogen Fixation

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posted on 03.07.2013, 00:00 by Andrew J. Keane, Peter Y. Zavalij, Lawrence R. Sita
Chemical reduction of the Ta­(V) hydrazido chloride 1 generates the open-shell, mononuclear Ta­(IV) hydrazido complex 2, which upon N-methylation yields the corresponding structurally characterized Ta­(IV) hydrazidium 6. Chemical reduction of 6 results in N–N bond cleavage to generate a cis/trans mixture of the [Ta­(V),Ta­(V)] bis­(μ-nitrido) product 7 in tetrahydrofuran and the mononuclear Ta­(V) parent imide 8 in toluene. These results serve to establish an important foundation for the pursuit of a group-5 metal variant of the Schrock cycle for dinitrogen fixation.