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Coordination Microenvironment-Driven Frontier Orbital Modulation for Dinitrogen Capture in Acetylphenol-Ligated
Zicheng Zhao1, Zhonghuan Lai1, Kairui Yang1
1State Key Laboratory of Elemento-Organic Chemistry and Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin 300071, China.
The Journal of Physical Chemistry Letters
|June 5, 2026
Summary
Ligand coordination environments critically influence catalyst activity. Oxygen-coordinated cobalt complexes efficiently capture dinitrogen (N2) at room temperature, unlike inert sulfur-coordinated analogues, due to modulated frontier orbitals.
Area of Science:
- Catalysis
- Materials Science
- Computational Chemistry
Background:
- Rational catalyst design requires understanding how coordination microenvironments affect molecular activation.
- Dinitrogen (N2) capture and fixation are crucial for industrial processes and nitrogen cycle research.
Purpose of the Study:
- To elucidate the mechanism by which coordination microenvironments govern N2 capture in mononuclear cobalt cations.
- To investigate the role of frontier orbital modulation in dictating catalytic activity.
Main Methods:
- Reaction mass spectrometry was employed to study N2 capture activity.
- Density functional theory (DFT) calculations, including frontier molecular orbital and natural bond orbital analyses, were used to understand the electronic structure and bonding.
Main Results:
- Oxygen-coordinated cobalt complexes ([Co(Hap)]+ and [Co(Dhap)]+) exhibited significant room-temperature N2 capture.
- Sulfur-coordinated cobalt complex ([Co(Map)]+) showed no N2 capture activity.
- DFT analysis revealed that O-coordination leads to symmetry-matched LUMO for N2 fixation, while S-coordination results in LUMO energy level inversion and disruption of orbital matching.
Conclusions:
- Ligand coordination environment dictates N2 capture activity through frontier orbital modulation.
- Strong electron donation from sulfur ligands destabilizes metal-centered orbitals, hindering N2 fixation.
- This study provides fundamental physicochemical guidelines for designing efficient N2-fixation catalysts.
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