ja402804k_si_006.cif (28.68 kB)
N–N Bond Cleavage of Mid-Valent Ta(IV) Hydrazido and Hydrazidium Complexes Relevant to the Schrock Cycle for Dinitrogen Fixation
dataset
posted on 2013-07-03, 00:00 authored by Andrew
J. Keane, Peter Y. Zavalij, Lawrence R. SitaChemical
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.