Amidinatogermylene Metal Complexes as Homogeneous Catalysts in Alcoholic Media

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• 作者：Lucía Álvarez-Rodríguez ; Javier A. Cabeza ; José M. Fernández-Colinas ; Pablo García-Álvarez ; Diego Polo
• 刊名：Organometallics
• 出版年：2016
• 出版时间：August 8, 2016
• 年：2016
• 卷：35
• 期：15
• 页码：2516-2523
• 全文大小：477K
• 年卷期：0
• ISSN：1520-6041

文摘

A series of transition-metal complexes containing the bulky amidinatogermylene Ge(^tBu₂bzam)^tBu (1; ^tBu₂bzam = N,N′-bis(tert-butyl)benzamidinate) as a ligand have been prepared and characterized. While the hydrolytic degradation of the germylene ligand of the square-planar complexes [MCl(η⁴-cod){Ge(^tBu₂bzam)^tBu}] (M = Rh (2), Ir (3); cod = 1,5-cyclooctadiene) and [PdCl(η³-metallyl){Ge(^tBu₂bzam)^tBu}] (4; metallyl = 2-methylallyl) is slow but clearly evident in carefully dried aprotic solvents, the octahedral complexes [RuCl₂(η⁶-cym){Ge(^tBu₂bzam)^tBu}] (5; cym = p-cymene) and [IrCl₂(η⁵-Cp*){Ge(^tBu₂bzam)^tBu}] (6; Cp* = pentamethylcyclopentadienyl) have proven to be stable even in alcoholic solvents. These latter complexes have been tested as catalyst precursors of reactions involving alcohols as substrates and/or solvents, and remarkably, they have been found to be active in the transfer hydrogenation of cyclohexanone with isopropyl alcohol (5 and 6), the N-alkylation of aniline with benzyl alcohol (5 and 6), and the deuteriation of acetophenone with CD₃OD (6). The use of heavier carbene metal complexes as catalyst precursors of reactions involving alcohols as solvents is unprecedented.