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1,2‐migration in N ‐phosphano functionalized N ‐heterocyclic carbenes
Author(s) -
Kirilchuk Andrey A.,
Yurchenko Aleksandr A.,
Kostyuk Aleksandr N.,
Rozhenko Alexander B.
Publication year - 2015
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.23767
Subject(s) - intramolecular force , carbene , chemistry , intermolecular force , density functional theory , singlet state , computational chemistry , nucleophile , transition state , catalysis , stereochemistry , molecule , organic chemistry , physics , nuclear physics , excited state
1,2‐Migration of the phosphano‐group to the carbene center in N ‐phosphano functionalized N ‐heterocyclic carbenes has been studied by density functional theory (DFT) calculations. An intramolecular mechanism with a three‐center transition state structure seems to be most plausible for the isolated carbenes, while an intermolecular pathway catalyzed by azolium salts may be preferable for a migration proceeding in the course of generating the carbenes in situ . Our calculations show that amino‐substitution at the phosphorus atom and an enhanced nucleophilicity of the heterocycle scaffold facilitate the phosphorus shift. Calculated singlet‐triplet energy gaps do not correlate with thermodynamic stability of the studied carbenes and their disposition toward the 1,2‐rearrangement. © 2014 Wiley Periodicals, Inc.