P鈥揘/P鈥揚 Bond Metathesis for the Synthesis of Complex Polyphosphanes

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• 作者：Kai-Oliver Feldmann ; Jan J. Weigand
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：September 19, 2012
• 年：2012
• 卷：134
• 期：37
• 页码：15443-15456
• 全文大小：827K
• 年卷期：v.134,no.37(September 19, 2012)
• ISSN：1520-5126

文摘

A unique hexaphosphane featuring a 2,2鈥?bi(1,2,3-triphosphacyclopentane) moiety (19) and an ethylene-bridged bis-isotetraphosphane (27^c,m) were both selectively prepared in efficient one-pot syntheses from easily accessible tris(3,5-dimethyl-1-pyrazolyl)phosphane (14) and 1,2-bis(phenylphosphanyl)ethane (18^c,m). The formation of 27^c,m is an example of a highly efficient P鈥揚 bond formation via protolysis. In contrast, the formation of 19 comprises P鈥揘/P鈥揚 bond metathesis steps. This constitutes a novel synthetic approach toward the preparation of complex polyphosphanes. Detailed spectroscopic investigations form the basis for a mechanistic understanding of this unprecedented methodology. Furthermore, the preparation of a unique dinuclear iron鈥揷arbonyl complex which features hexaphosphane 19 as a bridging ligand illustrates the potential use of complex polyphosphanes such as 19 as ligands in transition metal chemistry.