Journal
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
Volume 116, Issue 43, Pages 21416-21420Publisher
NATL ACAD SCIENCES
DOI: 10.1073/pnas.1913664116
Keywords
gas-phase catalysis; dinitrogen activation; metal nitride; active site; Mars/van Krevelen mechanism
Categories
Funding
- German Research Foundation Germany's Excellence Strategy [EXC 2008/1-390540038]
- Fonds der Chemischen Industrie
- National Natural Science Foundation of China [21473070, 21773085]
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An unprecedented, spontaneous, and complete cleavage of the triple bond of N-2 in the thermal reaction of N-15(2) with Ta-2 N-14(+) was observed experimentally by Fourier transform ion cyclotron resonance mass spectrometry; mechanistic aspects of the degenerate ligand exchange were addressed by high-level quantum chemical calculations. The hidden dis- and reassembly of N-2, mediated by Ta2N+, constitutes a full catalytic cycle. A frontier orbital analysis reveals that the scission of the N-2 triple bond is essentially governed by the donation of d-electrons from the 2 metal centers into antibonding pi*-orbitals of N-2 and by the concurrent migration of electrons from bonding pi- and sigma-orbitals of N-2 into empty d-orbitals of the metals. This work may contribute to a rational design of catalysts in order to reduce the still enormous energy demand required for an artificial dinitrogen activation.
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