Cleavage of Both C(sp3)−C(sp2) Bonds of Alkylidenecyclopropanes: Formation of Ethylene−Osmium−Vinylidene Complexes

The complex [OsTp(κ1-OCMe)2(PiPr3)]BF4 [Tp = hydridotris(pyrazolyl)borate] promotes the cleavage of both C(sp3)−C(sp2) bonds of benzylidenecyclopropane and 3-phenylpropylidenecyclopropane to yield the complexes [OsTp(CCHR)(η2-CH2CH2)(PiPr3)]BF4 (R = Ph, CH2CH2Ph). The process is proposed to take...

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Veröffentlicht in:	Journal of the American Chemical Society 2010-01, Vol.132 (2), p.454-455
Hauptverfasser:	Castro-Rodrigo, Ruth, Esteruelas, Miguel A, López, Ana M, López, Fernando, Mascareñas, José L, Oliván, Montserrat, Oñate, Enrique, Saya, Lucía, Villarino, Lara
Format:	Artikel
Sprache:	eng
Schlagworte:	Crystallography, X-Ray Cyclopropanes - chemistry Ethylenes - chemistry Models, Molecular Molecular Conformation Organometallic Compounds - chemistry Osmium - chemistry Stereoisomerism Thermodynamics Vinyl Compounds - chemistry
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Beschreibung
Zusammenfassung:	The complex [OsTp(κ1-OCMe)2(PiPr3)]BF4 [Tp = hydridotris(pyrazolyl)borate] promotes the cleavage of both C(sp3)−C(sp2) bonds of benzylidenecyclopropane and 3-phenylpropylidenecyclopropane to yield the complexes [OsTp(CCHR)(η2-CH2CH2)(PiPr3)]BF4 (R = Ph, CH2CH2Ph). The process is proposed to take place via metallacyclopropene intermediates stabilized by an ethylene chelation assistant. The driving force for the fragmentation is the high stability of the resulting ethylene−Os−vinylidene species.
ISSN:	0002-7863 1520-5126
DOI:	10.1021/ja909240q