Document Detail

Mixed (PS/PO)-Stabilized Geminal Dianion: Facile Diastereoselective Intramolecular CH Activations by a Related Ruthenium-Carbene Complex.
MedLine Citation:
PMID:  23136126     Owner:  NLM     Status:  Publisher    
A new unsymmetrical geminal dianion that contained both a phosphine oxide moiety and a phosphine sulfide moiety has been synthesized. Its reactivity towards Ru(II) was explored, which led to the formation of a highly reactive carbene complex that evolved at room temperature to yield a kinetic orthometalated Ru(II) complex through CH activation of the phenyl group of the phosphine oxide moiety. This insertion was found to be thermally reversible and a second CH insertion occurred at a phenyl group of the phosphine sulfide moiety to form the thermodynamic orthometalated Ru(II) complex in a diastereospecific manner. DFT calculations fully rationalized the experimental findings in terms of the relative energies of the kinetic and thermodynamic products and allowed the mechanism of this process to be fully understood.
Hadrien Heuclin; Xavier F Le Goff; Nicolas Mézailles
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-11-7
Journal Detail:
Title:  Chemistry (Weinheim an der Bergstrasse, Germany)     Volume:  -     ISSN:  1521-3765     ISO Abbreviation:  Chemistry     Publication Date:  2012 Nov 
Date Detail:
Created Date:  2012-11-8     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9513783     Medline TA:  Chemistry     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Copyright Information:
Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Laboratoire Hétéroéléments et Coordination, Ecole Polytechnique, CNRS, Route de Saclay, 91120 Palaiseau (France).
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