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Mixed (PS/PO)‐Stabilized Geminal Dianion: Facile Diastereoselective Intramolecular CH Activations by a Related Ruthenium–Carbene Complex
Author(s) -
Heuclin Hadrien,
Le Goff Xavier F.,
Mézailles Nicolas
Publication year - 2012
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.201202680
Subject(s) - moiety , carbene , chemistry , intramolecular force , geminal , phosphine , reactivity (psychology) , ruthenium , phosphine oxide , medicinal chemistry , sulfide , photochemistry , stereochemistry , organic chemistry , catalysis , medicine , alternative medicine , pathology
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.