Theoretical study on activation and protonation of dinitrogen on Cubane-Type MIr3S4 Clusters (M = V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ru, and W)

Hiromasa Tanaka, Fumihiro Ohsako, Hidetake Seino, Yasushi Mizobe, Kazunari Yoshizawa

Research output: Contribution to journalArticle

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Abstract

Density functional theory (DFT) calculations on cubane-type metal-sulfido clusters MIr3S4 ligating N2 (M = V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ru, and W) have been performed for the proposal of new clusters that can highly activate N2 beyond the RuIr3S4 cluster prepared by Mizobe and co-workers [Angew. Chem. Int. Ed. 2007, 46, 5431]. The degree of N2 activation in the metal-N2 complexes was evaluated based on the N-N bond distance and vibrational frequency and the gross atomic charge on N2. The degree of N2 activation strongly depends on the metal atoms at the N2-binding site, and the MoIr3S4 and Wlr3S4 clusters exhibit significant N2-activation ability. The reactivity of the MIr3S4-N2 complexes (M = Ru, Mo, and W) with a proton donor (lutidinium) has been discussed from a kinetic aspect by exploring a possible reaction pathway of proton transfer. The protonation of the Ru-N2 complex would not occur due to a very high-activation barrier and to an instability of the Ru-NNH+ complex, which is consistent with our present experimental result that the Ru-N2 complex has not been protonated at room temperature. On the other hand, the protonation of the Mo-N2 and W-N2 complexes would proceed smoothly from DFT criteria. The result of calculations indicates that the Mo and W clusters are best suited for the protonation of N2, which is the first step toward nitrogen fixation.

Original languageEnglish
Pages (from-to)2464-2470
Number of pages7
JournalInorganic Chemistry
Volume49
Issue number5
DOIs
Publication statusPublished - Mar 1 2010

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cubane
Protonation
Chemical activation
activation
Density functional theory
Metals
Nitrogen fixation
nitrogenation
density functional theory
Proton transfer
protons
Vibrational spectra
metal clusters
Metal complexes
metals
Protons
proposals
reactivity
Binding Sites
Atoms

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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Theoretical study on activation and protonation of dinitrogen on Cubane-Type MIr3S4 Clusters (M = V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ru, and W). / Tanaka, Hiromasa; Ohsako, Fumihiro; Seino, Hidetake; Mizobe, Yasushi; Yoshizawa, Kazunari.

In: Inorganic Chemistry, Vol. 49, No. 5, 01.03.2010, p. 2464-2470.

Research output: Contribution to journalArticle

Tanaka, Hiromasa ; Ohsako, Fumihiro ; Seino, Hidetake ; Mizobe, Yasushi ; Yoshizawa, Kazunari. / Theoretical study on activation and protonation of dinitrogen on Cubane-Type MIr3S4 Clusters (M = V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ru, and W). In: Inorganic Chemistry. 2010 ; Vol. 49, No. 5. pp. 2464-2470.
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