Abstract
In this paper, we present a DFT study of the proton reduction mechanism catalyzed by the complex [Ni(P2 HN2 H)2]2+, bioinspired from the hydrogenases. A detailed analysis of the reactive isomers is discussed together with the localizations of the transitions states and energy minima. The reactive catalytic species is a biprotonated Ni(0) complex that can show different conformations and that can be protonated on different sites. The energies of the different conformations and biprotonated species have been calculated and discussed. Energy barriers for two different reaction mechanisms have been identified in solvent and in gas phase. Frequency calculations have been performed to check the nature of the energy minima and for the calculations of entropic energetic terms and zero point energies. We show that only one conformation is mostly reactive. All the others species are nonreactive in their original form, and they have to pass through conformational barriers in order to transform in the reactive species.
| Original language | English |
|---|---|
| Pages (from-to) | 11861-11867 |
| Number of pages | 7 |
| Journal | Journal of Physical Chemistry A |
| Volume | 114 |
| Issue number | 43 |
| DOIs | |
| Publication status | Published - 4 Nov 2010 |
| Externally published | Yes |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
Cite this
New insights in the electrocatalytic proton reduction and hydrogen oxidation by bioinspired catalysts : A DFT investigation. / Kachmar, Ali; Vetere, Valentina; Maldivi, Pascale; Franco, Alejandro A.
In: Journal of Physical Chemistry A, Vol. 114, No. 43, 04.11.2010, p. 11861-11867.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - New insights in the electrocatalytic proton reduction and hydrogen oxidation by bioinspired catalysts
T2 - A DFT investigation
AU - Kachmar, Ali
AU - Vetere, Valentina
AU - Maldivi, Pascale
AU - Franco, Alejandro A.
PY - 2010/11/4
Y1 - 2010/11/4
N2 - In this paper, we present a DFT study of the proton reduction mechanism catalyzed by the complex [Ni(P2 HN2 H)2]2+, bioinspired from the hydrogenases. A detailed analysis of the reactive isomers is discussed together with the localizations of the transitions states and energy minima. The reactive catalytic species is a biprotonated Ni(0) complex that can show different conformations and that can be protonated on different sites. The energies of the different conformations and biprotonated species have been calculated and discussed. Energy barriers for two different reaction mechanisms have been identified in solvent and in gas phase. Frequency calculations have been performed to check the nature of the energy minima and for the calculations of entropic energetic terms and zero point energies. We show that only one conformation is mostly reactive. All the others species are nonreactive in their original form, and they have to pass through conformational barriers in order to transform in the reactive species.
AB - In this paper, we present a DFT study of the proton reduction mechanism catalyzed by the complex [Ni(P2 HN2 H)2]2+, bioinspired from the hydrogenases. A detailed analysis of the reactive isomers is discussed together with the localizations of the transitions states and energy minima. The reactive catalytic species is a biprotonated Ni(0) complex that can show different conformations and that can be protonated on different sites. The energies of the different conformations and biprotonated species have been calculated and discussed. Energy barriers for two different reaction mechanisms have been identified in solvent and in gas phase. Frequency calculations have been performed to check the nature of the energy minima and for the calculations of entropic energetic terms and zero point energies. We show that only one conformation is mostly reactive. All the others species are nonreactive in their original form, and they have to pass through conformational barriers in order to transform in the reactive species.
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UR - http://www.scopus.com/inward/citedby.url?scp=78049492296&partnerID=8YFLogxK
U2 - 10.1021/jp107104k
DO - 10.1021/jp107104k
M3 - Article
VL - 114
SP - 11861
EP - 11867
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 43
ER -