Complete cleavage of the N≡N triple bond by Ta2N+ via degenerate ligand exchange at ambient temperature: A perfect catalytic cycle.
Caiyun GengJilai LiThomas WeiskeHelmut SchwarzPublished in: Proceedings of the National Academy of Sciences of the United States of America (2019)
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 π*-orbitals of N2 and by the concurrent migration of electrons from bonding π- and σ-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.
Keyphrases
- density functional theory
- molecular dynamics
- mass spectrometry
- transition metal
- energy transfer
- air pollution
- dna binding
- particulate matter
- liquid chromatography
- electron transfer
- high resolution
- highly efficient
- molecular dynamics simulations
- climate change
- monte carlo
- human health
- metal organic framework
- transcription factor
- rectal cancer