Synthesis and structure of orthopalladated complexes derived from prochiral iminophosphoranes and phosphorus ylides

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• 作者：David Aguilar ; Miguel Angel Aragü ; é ; s ; Raquel Bielsa ; Elena Serrano ; Tatiana Soler ; Rafael Navarro ; Esteban P. Urriolabeitia
• 关键词：Cyclometallated ; CH-bond activation ; Iminophosphoranes ; Phosphorus ylides ; Palladium
• 刊名：Journal of Organometallic Chemistry
• 出版年：2008
• 出版时间：1 February 2008
• 年：2008
• 卷：693
• 期：3
• 页码：417-424
• 全文大小：241 K

文摘

The iminophosphorane Ph₂MePp://www.sciencedirect.com/scidirimg/entities/dbnd"" alt=""double bond; length as m-dash"" border=0>NPh (1) reacts with Pd(OAc)₂ to give the orthopalladated [Pd(μ-Cl){C₆H₄(PPh(Me)p://www.sciencedirect.com/scidirimg/entities/dbnd"" alt=""double bond; length as m-dash"" border=0>NPh-κ-C,N)-2}]₂ (2) as the racemic mixture, which reacts with Tl(acac) to give [Pd(acac){C₆H₄(PPh(Me)p://www.sciencedirect.com/scidirimg/entities/dbnd"" alt=""double bond; length as m-dash"" border=0>NPh-κ-C,N)-2}] (3). The X-ray structure of (3) has been determined by diffraction methods. The phosphorus ylide Ph₂MePp://www.sciencedirect.com/scidirimg/entities/dbnd"" alt=""double bond; length as m-dash"" border=0>CHC(O)Ph (5) reacts with Pd(OAc)₂ to give the dinuclear [Pd(μ-Cl){C₆H₄(PPh(Me)CHC(O)Ph-κ-C,C)-2}]₂ (6) as a mixture of isomers. Complex (6) reacts with Tl(acac), PPh₃ or AgClO₄/dppe giving the mononuclear derivatives [Pd(acac){C₆H₄(PPh(Me)CHC(O)Ph-κ-C,C)-2}] (7), [PdCl{C₆H₄(PPh(Me)CHC(O)Ph-κ-C,C)-2}PPh₃] (8) and [Pd{C₆H₄(PPh(Me)CHC(O)Ph-κ-C,C)-2}(dppe–P,P′)](ClO₄) (9), as mixtures of stereoisomers with high diastereomeric excess.