Reactive Indolyl Complexes of Group 9 Metals

详细信息    查看全文

• 作者：Joanne Hui Hui Ho ; David St Clair Black ; Barbara Ann Messerle ; Jack Kay Clegg ; Peter Turner
• 刊名：Organometallics
• 出版年：2006
• 出版时间：November 20, 2006
• 年：2006
• 卷：25
• 期：24
• 页码：5800 - 5810
• 全文大小：232K
• 年卷期：v.25,no.24(November 20, 2006)
• ISSN：1520-6041

文摘

A series of novel indolyl-imine ligand precursors have been synthesized. In particular, bidentate,tridentate, and potentially tetradentate ligands were prepared, each containing both indolyl sp²-N andimine sp²-N donors. A series of neutral rhodium(I) and iridium(I) complexes of these ligands weresynthesized, including monometallic and bimetallic complexes. The X-ray structures of three of themonometallic complexes with bidentate indolyl-imine ligands were determined. In each complex, themetal center was in a square planar conformation, as expected for Rh(I) and Ir(I) complexes. The five-and six-membered metallocycles formed on complexation of the metal with the ligands were all planar,and the aromaticity of the ligands was maintained. The Rh(I) complex with the tridentate indolyl ligand(L) reacted at room temperature with CH₂Cl₂ to form the Rh(III) chloromethyl complex [Rh(L)(CO)(CH₂Cl)(Cl)] via oxidative addition of the C-Cl bond of CH₂Cl₂. The Rh/Ir(I) indolyl-imine complexesare efficient catalysts for the intramolecular cyclization of 4-pentynoic acid to form -methylene--butyrolactone. A dinuclear Rh(I) complex was the most active catalyst, demonstrating a significant degreeof bimetallic cooperativity.