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Complete cleavage of the N?N triple bond by Ta2N+ via degenerate ligand exchange at ambient temperature: A perfect catalytic cycle.

ABSTRACT: An unprecedented, spontaneous, and complete cleavage of the triple bond of N2 in the thermal reaction of 15N2 with Ta2 14N+ 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 N2, mediated by Ta2N+, constitutes a full catalytic cycle. A frontier orbital analysis reveals that the scission of the N2 triple bond is essentially governed by the donation of d-electrons from the 2 metal centers into antibonding ?*-orbitals of N2 and by the concurrent migration of electrons from bonding ?- and ?-orbitals of N2 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.

SUBMITTER: Geng C 

PROVIDER: S-EPMC6815182 | biostudies-literature | 2019 Oct

REPOSITORIES: biostudies-literature

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Complete cleavage of the N≡N triple bond by Ta<sub>2</sub>N<sup>+</sup> via degenerate ligand exchange at ambient temperature: A perfect catalytic cycle.

Geng Caiyun C   Li Jilai J   Weiske Thomas T   Schwarz Helmut H  

Proceedings of the National Academy of Sciences of the United States of America 20191007 43

An unprecedented, spontaneous, and complete cleavage of the triple bond of N<sub>2</sub> in the thermal reaction of <sup>15</sup>N<sub>2</sub> with Ta<sub>2</sub><sup>14</sup>N<sup>+</sup> 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<sub>2</sub>, mediated by Ta<sub>2</sub>N<sup>+</sup>, constitutes a  ...[more]

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