2019 chapter

Toward N—N Bond Cleavage: Synthesis and Reactivity of Group 7 Dinitrogen Complexes

In Y. Nishibayashi (Ed.), Transition Metal‐Dinitrogen Complexes: Preparation and Reactivity (pp. 271–284).

By: E. Ison n

co-author countries: United States of America 🇺🇸

Ed(s): Y. Nishibayashi

Source: NC State University Libraries
Added: March 5, 2021

By far, the most commonly encountered group 7 dinitrogen (N2) complexes involve terminal N2 ligands. The majority of these molecules incorporate rhenium, with sporadic examples of complexes with manganese and to a lesser extent technetium. Complexes incorporating cyclopentadienyl (Cp) and its derivatives were also synthesized from strong reducing agents. Terminal nitrogen complexes have been shown to react with transition metals to form bridged dinitrogen complexes. This chapter outlines two examples where a coordinated N2 ligand has been reduced. For N2 cleavage, the density functional theory (DFT) calculations suggest that the transition state for this reaction contains a zigzag structure similar to the molybdenum complex reported by Cummins and coworkers. Given that both terminal and bridged N2 complexes are known, and at least in one case, a bridged dinitrogen complex is proposed to lead to N2 cleavage, the prospect for catalytic N2 activation with group 7 is still promising.