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Silyl group migration in a P-silylated phosphonium ylide derived from dppm — A combined experimental and theoretical study

Publication date: June 2013
Source:Inorganic Chemistry Communications, Volume 32

Author(s): Jens Langer , Villö K. Pálfi , Björn Schowtka , Helmar Görls , Markus Reiher

The lithium complex [(Et2O)2Li{(Ph2P)2CH}] (2) was synthesized by recrystallization of the corresponding solvent-free complex in diethyl ether. The kinetic product of the reaction of 2 and Me3SiCl, Ph2PCHP(SiMe3)Ph2 (3), was isolated under appropriate conditions and characterized by NMR measurement at 228K. Both, reversible P-to-P and irreversible P-to-C migration of the silyl group were observed at higher temperatures and investigated by NMR techniques and quantum chemical calculations. The thermodynamic product Ph2PCH(SiMe3)PPh2 (1) was found to be 84kJmol−1 (B97-D/TZVPP) lower in energy than the kinetic product 3. The molecular structures of 1–3 were determined by X-ray diffraction measurement.
Graphical abstract



Authors:   Author(s): Jens Langer , Villö K. Pálfi , Björn Schowtka , Helmar Görls , Markus Reiher
Journal:   Inorganic Chemistry Communications
Year:   2013
DOI:   10.1016/j.inoche.2013.03.008
Publication date:   15-Apr-2013
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