| Mixed (PS/PO)-Stabilized Geminal Dianion: Facile Diastereoselective Intramolecular CH Activations by a Related Ruthenium-Carbene Complex. | |
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MedLine Citation:
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PMID: 23136126 Owner: NLM Status: Publisher |
Abstract/OtherAbstract:
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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 CH activation of the phenyl group of the phosphine oxide moiety. This insertion was found to be thermally reversible and a second CH 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. |
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Authors:
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Hadrien Heuclin; Xavier F Le Goff; Nicolas Mézailles |
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Publication Detail:
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Type: JOURNAL ARTICLE Date: 2012-11-7 |
Journal Detail:
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Title: Chemistry (Weinheim an der Bergstrasse, Germany) Volume: - ISSN: 1521-3765 ISO Abbreviation: Chemistry Publication Date: 2012 Nov |
Date Detail:
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Created Date: 2012-11-8 Completed Date: - Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 9513783 Medline TA: Chemistry Country: - |
Other Details:
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Languages: ENG Pagination: - Citation Subset: - |
Copyright Information:
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Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. |
Affiliation:
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Laboratoire Hétéroéléments et Coordination, Ecole Polytechnique, CNRS, Route de Saclay, 91120 Palaiseau (France). |
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From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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