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How to Make the σ(0)π(2) Singlet the Ground State of Carbenes.
MedLine Citation:
PMID:  24007553     Owner:  NLM     Status:  Publisher    
Successful strategies have previously been developed to stabilize the σ(2)π(0) singlet states of carbenes, relative to σ(1)π(1) triplet states. However, little or no attention has been paid to the stabilization of the σ(0)π(2) singlet states. We present two simple strategies to stabilize the σ(0)π(2) singlet states of carbenes, relative to both the σ(2)π(0) singlet and σ(1)π(1) triplet states. These strategies consist of destabilization of the carbene σ orbital by two, adjacent, sp(2) nitrogen lone pairs of electrons and stabilization of the carbene 2p-π orbital by incorporating it into a five-membered ring, containing two double bonds, or into a six-membered ring, containing two double bonds and a sixth atom that has a low-lying empty π orbital. B3LYP, CASPT2, and CCSD(T) calculations have been performed in order to assess the success of these strategies in creating derivatives of cyclopenta-2,4-dienylidene and cyclohexa-2,5-dienylidene with σ(0)π(6) singlet ground states. Differences between the calculated geometries and binding energies of the Xe complexes of the σ(0)π(6) singlet ground state of 2,5-diazacyclopentadienylidene (5) and the σ(2)π(0) singlet states of CH2 and CF2 are discussed.
Bo Chen; Andrey Yu Rogachev; David A Hrovat; Roald Hoffmann; Weston Thatcher Borden
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2013-9-5
Journal Detail:
Title:  Journal of the American Chemical Society     Volume:  -     ISSN:  1520-5126     ISO Abbreviation:  J. Am. Chem. Soc.     Publication Date:  2013 Sep 
Date Detail:
Created Date:  2013-9-6     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  7503056     Medline TA:  J Am Chem Soc     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Department of Chemistry and the Center for Advanced, Scientific Computing and Modeling, University of North Texas , 1155 Union Circle, #305070, DentonTexas, 76203-5070, United States.
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