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Resonance theory of catalytic action of transition‐metal complexes: Isomerization of quadricyclane to norbornadiene catalyzed by metal porphyrins
Author(s) -
Tchougréeff Andrei L.,
Tokmachev Andrei M.,
Dronskowski Richard
Publication year - 2013
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.24386
Subject(s) - norbornadiene , isomerization , quadricyclane , catalysis , chemistry , transition metal , photochemistry , computational chemistry , valence (chemistry) , organic chemistry
The theory of catalytic activity of transition‐metal compounds is a fascinating problem especially if a comparison of different catalysts is necessary. The isomerization of quadricyclane (QC) to norbornadiene (NB) catalyzed by transition‐metal porphyrins is a challenge and incidentally a suitable benchmark for various theories of catalysis. We analyze this process in detail using a valence bond‐like scheme adjusted for the description of reaction centers containing transition‐metal atoms. A qualitative explanation of contrasting catalytic behavior of Mn‐phthalocyanine and Co‐tetraphenylporphyrin is obtained from the analysis of the spectra of local many electron states of free catalysts and their complexes with the reactant/product. This picture is supported by the numerical analysis of potential energy profiles for the QC to NB isomerization in the presence of a catalyst performed in the effective Hamiltonian approximation. This exemplary reaction is put in a more general perspective of theories of catalytic activity of transition‐metal complexes and in relation with oxygenation reactions. © 2013 Wiley Periodicals, Inc.