Nitrogen Fixation Catalyzed by Dinitrogen-Bridged Dimolybdenum Complexes Bearing PCP- and PNP-Type Pincer Ligands: A Shortcut Pathway Deduced from Free Energy Profiles

Akihito Egi, Hiromasa Tanaka, Asuka Konomi, Yoshiaki Nishibayashi, Kazunari Yoshizawa

Research output: Contribution to journalArticlepeer-review

2 Citations (Scopus)

Abstract

Density-functional-theory (DFT) calculations are carried out for the proposal of a theoretically-plausible reaction pathway for nitrogen fixation catalyzed by dinitrogen-bridged dimolybdenum complexes bearing pincer-type PCP and PNP ligands. The free energy profiles of the entire reaction pathway calculated with a dispersion-corrected functional provide a catalytic mechanism energetically more efficient than the previously proposed one [Nat. Commun. 2014, 5, 3737]. In the newly-proposed mechanism the dinuclear Mo–N≡N–Mo structure should be maintained during the catalytic cycle. Despite the coordination of the triflate group with a strong electron-withdrawing ability, dinitrogen coordinated to a MoI center has higher reactivity with a proton donor than that coordinated to an electron-rich Mo0 center. The calculated results enable us to propose a shortcut pathway in which the regeneration of the dimolybdenum Mo0Mo0 complex is not required. Intermetallic electron transfer between the two Mo centers induced by protonation effectively enhances the reactivity of coordinate N2 with a proton donor. Our calculations reveal that the synergy of the Mo centers at the protonation step is essential for the catalytic performance of the dimolybdenum system.

Original languageEnglish
Pages (from-to)1490-1498
Number of pages9
JournalEuropean Journal of Inorganic Chemistry
Volume2020
Issue number15-16
DOIs
Publication statusPublished - Apr 30 2020

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

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