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Silavinylidene Stabilized by an N‐Heterocyclic Carbene: A Theoretically Predicted Stable Molecule
Author(s) -
Xu Jing,
Ding YiHong,
Andrada Diego M.,
Frenking Gernot
Publication year - 2014
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.201403252
Subject(s) - carbene , substituent , chemistry , singlet state , molecule , acceptor , excited state , stereochemistry , crystallography , catalysis , physics , organic chemistry , atomic physics , condensed matter physics
Quantum chemical calculations show that the N‐heterocyclic carbene (NHC)‐stabilized silavinylidene, NHC t Bu →CSiR 2 is a strongly bonded complex, which has a linear arrangement of the donor and acceptor moieties. The molecule is the energetically lowest lying isomer of the NHC‐stabilized R 2 CSi isomers and it is stable towards dimerization when R is a bulky substituent. The silavinylidene complex is the only species of the silylidene homologues NHC t Bu →EE′R 2 (E, E′=C–Pb) which possesses a linear arrangement. The unusual bonding situation is explained in terms of donor–acceptor interactions between NHC t Bu as σ donor and CSiR 2 in the doubly excited singlet state 3a 1 ⇒2b 2 which leads to a significantly shorter CSiR 2 bond compared with free CSiR 2 .