On the Mechanism of Dihydrogen Activation by Frustrated Lewis Pairs. Insights from the Analysis of Domain Averaged Fermi Holes and Generalized Population Analysis

Kód výsledku v IS VaVaI

RIV/67985858:_____/13:00391472 - isvavai.cz

Výsledek na webu

http://dx.doi.org/10.1021/jp312755z

DOI - Digital Object Identifier

10.1021/jp312755z

Jazyk výsledku

angličtina

Název v původním jazyce

On the Mechanism of Dihydrogen Activation by Frustrated Lewis Pairs. Insights from the Analysis of Domain Averaged Fermi Holes and Generalized Population Analysis

Popis výsledku v původním jazyce

The electron reorganization responsible for the facilitation of heterolytic splitting of H-H bond by frustrated Lewis pair (FLP) catalysts have been studied using the analysis of domain averaged Fermi holes and generalized population analysis. The analysis of electron structures of the species along the reaction path has revealed that the anticipated synchronicity of previously considered electron shifts of electron pair of ?HH bond to vacant orbital on B and from the lone pair on basic N site to antibonding ?HH* orbital is associated with the build up of extensive delocalized bonding that can conveniently be characterized in terms of multicenter bond indices. In addition, the detailed scrutiny of IRC-dependence of the 2-center bond indices of disappearing H-H bond resulted in the proposal of a simple heuristic measure of the efficiency of the FLP catalysts.

Název v anglickém jazyce

On the Mechanism of Dihydrogen Activation by Frustrated Lewis Pairs. Insights from the Analysis of Domain Averaged Fermi Holes and Generalized Population Analysis

Popis výsledku anglicky

The electron reorganization responsible for the facilitation of heterolytic splitting of H-H bond by frustrated Lewis pair (FLP) catalysts have been studied using the analysis of domain averaged Fermi holes and generalized population analysis. The analysis of electron structures of the species along the reaction path has revealed that the anticipated synchronicity of previously considered electron shifts of electron pair of ?HH bond to vacant orbital on B and from the lone pair on basic N site to antibonding ?HH* orbital is associated with the build up of extensive delocalized bonding that can conveniently be characterized in terms of multicenter bond indices. In addition, the detailed scrutiny of IRC-dependence of the 2-center bond indices of disappearing H-H bond resulted in the proposal of a simple heuristic measure of the efficiency of the FLP catalysts.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

GA203/09/0118: Moderní teoretické metody pro analýzu chemických vazeb

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2013

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of Physical Chemistry A

ISSN

1089-5639

e-ISSN

—

Svazek periodika

117

Číslo periodika v rámci svazku

12

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

8

Strana od-do

2656-2663

Kód UT WoS článku

000317032400027

EID výsledku v databázi Scopus

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