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Cycling between Molybdenum-Dinitrogen and -Nitride Complexes to Support the Reaction Pathway for Catalytic Formation
Kazuya Arashiba1, Hiromasa Tanaka2, Kazunari Yoshizawa3
1Department of Systems Innovation, School of Engineering, The University of Tokyo, Bunkyo-ku, Tokyo 1, 13-8656, Japan.
Abstract:
Cycling between molybdenum(I)-dinitrogen and molybdenum(IV)-nitride complexes was investigated under ambient reaction conditions. A kinetic study of the second-order reaction rate for the conversion of the molybdenum-dinitrogen complex into the molybdenum-nitride complex indicates that the formation of the dinitrogen-bridged dimolybdenum complex is involved in the rate-determining step. DFT calculations indicate that the molybdenum-dinitrogen complex transforms into the molybdenum-nitride complex via direct cleavage of the nitrogen-nitrogen triple bond of the bridging dinitrogen ligand of the dinitrogen-bridged dimolybdenum complex. The corresponding reaction of the molybdenum-nitride complex transforming into the molybdenum-dinitrogen complex proceeds via the ligand exchange of ammonia for dinitrogen at the dinitrogen-bridged dimolybdenum complexes. A new modified reaction pathway has been proposed based on the findings of our experimental and theoretical results.
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