Mixed (P=S/P=O)-Stabilized Geminal Dianion: Facile Diastereoselective Intramolecular C-H Activations by a Related Ruthenium-Carbene Complex

Hadrien Heuclin 1 X. Le Goff 1 Nicolas Mézailles 1, *
* Corresponding author
1 DCPH - Laboratoire Hétéroéléments et Coordination
Abstract : 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.
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Submitted on : Tuesday, November 19, 2013 - 10:24:22 AM
Last modification on : Tuesday, July 30, 2019 - 8:26:01 AM

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Hadrien Heuclin, X. Le Goff, Nicolas Mézailles. Mixed (P=S/P=O)-Stabilized Geminal Dianion: Facile Diastereoselective Intramolecular C-H Activations by a Related Ruthenium-Carbene Complex. Chemistry - A European Journal, Wiley-VCH Verlag, 2012, 18 (50), pp.16136-16144. ⟨10.1002/chem.201202680⟩. ⟨hal-00906024⟩

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