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Moving toward Ylide‐Stabilized Carbenes
Author(s) -
Borthakur Bitupon,
Phukan Ashwini K.
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201500860
Subject(s) - ylide , carbene , chemistry , singlet state , lone pair , atom (system on chip) , photochemistry , carbon atom , computational chemistry , crystallography , ring (chemistry) , medicinal chemistry , catalysis , atomic physics , organic chemistry , physics , molecule , excited state , computer science , embedded system
The effect of ylide substitution at the α position to the carbene carbon (C c ) atom on the stability and σ‐donating ability of a number of cyclic carbenes has been studied theoretically. The stabilities of all of the carbenes were investigated from an evaluation of their singlet–triplet energy gaps and stabilization energies. All carbenes were found to have a stable singlet state. The energy of the σ‐symmetric lone‐pair orbital at the C c atom increases as a result of the introduction of ylide centers near to the C c atom. This indicates an enhanced σ‐donating ability of the ylide‐containing carbenes. The calculated carbonyl‐stretching frequencies of the corresponding rhodium complexes, proton affinities, and nucleophilicity index values correlate well with the σ basicity of the carbenes.