DFT study on N2 activation by a hydride-bridged diniobium complex. N≡N Bond cleavage accompanied by H2 evolution

Hiromasa Tanaka, Yoshihito Shiota, Tsukasa Matsuo, Hiroyuki Kawaguchi, Kazunari Yoshizawa

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Abstract

Density functional theory (DFT) calculations have been performed for the investigation of a plausible mechanism of the triple bond cleavage of N 2 in a diniobium complex supported by tridentate aryloxide ligands, {Nbv(μ-N)2Nbv}2-. 22With the assumption of a tetrakis(μ-hydrido)diniobium complex {Nblv(μ-H)4Nblv}2- as an initial complex, the N≡N cleavage on the Nb2 core proceeds in four steps. Dinitrogen is coordinated to the {Nb'''-H)Nb'''} core in a side- on/end-on manner, accompanied by the reductive elimination of H2. The N≡N bond of dinitrogen is activated up to a single bond (formally N 24-) by the two Nb(lll) atoms, once it is bound to the Nb2 core. Two electrons are prepared for the cleavage of the N-N single bond through the μ-H migration to an N atom, leading to the formation of an Nb-Nb bond. The N-N bond is then dissociated by the two electrons that are shared between the two Nb atoms. Finally, {Nb(μ-N)2Nb} 2- is generated after H2 elimination in which the N-bonded H atom is coupled with the remaining μ-H atom. The final H2 elimination is calculated to be the rate-determining step.

Original languageEnglish
Pages (from-to)3875-3881
Number of pages7
JournalInorganic chemistry
Volume48
Issue number8
DOIs
Publication statusPublished - Apr 20 2009

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Hydrides
hydrides
Density functional theory
cleavage
Chemical activation
activation
density functional theory
Atoms
elimination
atoms
Electrons
electrons
Ligands
ligands
single bond

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

DFT study on N2 activation by a hydride-bridged diniobium complex. N≡N Bond cleavage accompanied by H2 evolution. / Tanaka, Hiromasa; Shiota, Yoshihito; Matsuo, Tsukasa; Kawaguchi, Hiroyuki; Yoshizawa, Kazunari.

In: Inorganic chemistry, Vol. 48, No. 8, 20.04.2009, p. 3875-3881.

Research output: Contribution to journalArticle

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N2 - Density functional theory (DFT) calculations have been performed for the investigation of a plausible mechanism of the triple bond cleavage of N 2 in a diniobium complex supported by tridentate aryloxide ligands, {Nbv(μ-N)2Nbv}2-. 22With the assumption of a tetrakis(μ-hydrido)diniobium complex {Nblv(μ-H)4Nblv}2- as an initial complex, the N≡N cleavage on the Nb2 core proceeds in four steps. Dinitrogen is coordinated to the {Nb'''-H)Nb'''} core in a side- on/end-on manner, accompanied by the reductive elimination of H2. The N≡N bond of dinitrogen is activated up to a single bond (formally N 24-) by the two Nb(lll) atoms, once it is bound to the Nb2 core. Two electrons are prepared for the cleavage of the N-N single bond through the μ-H migration to an N atom, leading to the formation of an Nb-Nb bond. The N-N bond is then dissociated by the two electrons that are shared between the two Nb atoms. Finally, {Nb(μ-N)2Nb} 2- is generated after H2 elimination in which the N-bonded H atom is coupled with the remaining μ-H atom. The final H2 elimination is calculated to be the rate-determining step.

AB - Density functional theory (DFT) calculations have been performed for the investigation of a plausible mechanism of the triple bond cleavage of N 2 in a diniobium complex supported by tridentate aryloxide ligands, {Nbv(μ-N)2Nbv}2-. 22With the assumption of a tetrakis(μ-hydrido)diniobium complex {Nblv(μ-H)4Nblv}2- as an initial complex, the N≡N cleavage on the Nb2 core proceeds in four steps. Dinitrogen is coordinated to the {Nb'''-H)Nb'''} core in a side- on/end-on manner, accompanied by the reductive elimination of H2. The N≡N bond of dinitrogen is activated up to a single bond (formally N 24-) by the two Nb(lll) atoms, once it is bound to the Nb2 core. Two electrons are prepared for the cleavage of the N-N single bond through the μ-H migration to an N atom, leading to the formation of an Nb-Nb bond. The N-N bond is then dissociated by the two electrons that are shared between the two Nb atoms. Finally, {Nb(μ-N)2Nb} 2- is generated after H2 elimination in which the N-bonded H atom is coupled with the remaining μ-H atom. The final H2 elimination is calculated to be the rate-determining step.

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