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Ylide stabilized carbenes: a computational study
Author(s) -
Haerizade Bibi Narjes,
Kassaee Mohammad Zaman,
Zandi Hassan,
Koohi Maryam,
Ahmadi Ali A.
Publication year - 2014
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3353
Subject(s) - ylide , chemistry , density functional theory , reactivity (psychology) , carbene , singlet state , photochemistry , nucleophile , isodesmic reaction , computational chemistry , sulfur , medicinal chemistry , organic chemistry , catalysis , excited state , medicine , physics , alternative medicine , pathology , nuclear physics
High‐level Density Functional Theory calculations, coupled with appropriate isodesmic reaction, are employed to investigate the effects of α‐carbon, ammonium, phosphorus, and sulfur ylides, cyclization , and unsaturation on the stability, multiplicity, and reactivity of novel singlet (S) and triplet (T) carbenes. Among them the highly π ‐donating α ‐ammonium ylide is found to exert the highest stabilizing effect on the carbenic center. α ‐Ammonium ylides resist dimerization and hydrogenation . They show wider singlet–triplet energy gap (Δ Ε S–T ), broader band gap (Δ Ε HOMO–LUMO ), and higher nucleophilicity compared to the reported stable N ‐heterocyclic carbenes. Aromatic cyclic unsaturated ammonium, phosphorus, and sulfur ylide carbenes appear more stable than their saturated cyclic analogs which are in turn more viable than their acyclic counterparts. Copyright © 2014 John Wiley & Sons, Ltd.