Enantiomerically Pure, Planar Chiral Cp*Ru Complexes: Synthesis, Molecular Structures, DFT and Coordination Properties

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• 作者：Julien Dubarle-Offner ; M. Rosa Axet ; Lise Marie Chamoreau ; Hani Amouri ; Andrew L. Cooksy
• 刊名：Organometallics
• 出版年：2012
• 出版时间：June 25, 2012
• 年：2012
• 卷：31
• 期：12
• 页码：4429-4434
• 全文大小：274K
• 年卷期：v.31,no.12(June 25, 2012)
• ISSN：1520-6041

文摘

Reaction of (S)-1-(2-chlorophenyl)ethanol with [Cp*Ru(CH₃CN)₃][OTf] provides the single diastereomer (Sp)-[Cp*Ru(畏⁶-(S)-1-(2-chlorophenyl)ethanol)][OTf] ((Sp,S)-1), in which the metal center is preferentially placed on one side of the arene ring. The other enantiomer (R)-1-(2-chlorophenyl)ethanol provides the planar chiral ruthenium compound (Rp,R)-1. The structures of both enantiomers were ascertained by single-crystal X-ray diffraction. These compounds can be used as precursors to prepare the enantiopure metalated phosphino ligands (Sp)-[Cp*Ru(畏⁶-(S)-1-(2-diphenylphosphinophenyl)ethanol)][OTf] ((Sp,S)-2) and (Rp)-[Cp*Ru(畏⁶-(R)-1-(2-diphenylphosphinophenyl)ethanol)][OTf] ((Rp,R)-2), in which the 鈭扨Ph₂ unit is attached to a chiral metalated 蟺-arene platform. The chiral planar phosphine ligands react with [AuCl(tht)] to give heterobinuclear gold complexes with planar chirality, [AuCl((Sp,S)-2)] ((Sp,S)-3) and [AuCl((Rp,R)-2)] ((Rp,R)-3), as confirmed by their CD traces. Our method provides an entry to the preparation of a wide range of optically pure coordination compounds with potentially important properties.