Synthesis and isomerisation of two metallated N,O-complexes of ruthenium: Models for the Murai reaction

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• 作者：Rodolphe F.R. Jazzar ; Maurizio Varrone ; Andrew D. Burrows ; Stuart A. Macgregor ; Mary F. Mahon and Michael K. Whittlesey
• 关键词：Ruthenium complexes ; Phosphine ligands ; Hydride ligands ; Cyclometallation ; Murai reaction ; Density functional theory
• 刊名：Inorganica Chimica Acta
• 出版年：2006
• 出版时间：1 February 2006
• 年：2006
• 卷：359
• 期：3
• 页码：815-820
• 全文大小：262 K

文摘

Two isomers of the N,O-coordinated acetylpyrrolyl complex [Ru(PPh₃)₂(CO)(NC₄H₃C(O)CH₃)H] {cis-N,H (1) and trans-N,H (2)} have been prepared as models for catalytic intermediates in the Murai reaction. Complex 2 isomerises to 1 upon heating via a dissociative pathway (ΔH^‡ = 195 ± 41 kJ mol⁻¹; ΔS^‡ = 232 ± 62 J mol⁻¹ K⁻¹); the mechanism of this process has been modeled using density functional calculations. Complex 2 displays moderate catalytic activity for the Murai coupling of 2′-methylacetophenone with trimethylvinylsilane, but 1 proved to be catalytically inactive under the same conditions.