Formation of Binuclear Ruthenium(II) Aqua Complexes and a Mononuclear Ammonia Complex Bearing P-P-O Facial Tridentate Ligands and Oxametallacycle Moieties

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• 作者：Fumiaki Tsunawaki ; Yasuyuki Ura ; Teruyuki Kondo ; Tomomichi Iwasa ; Tatsuro Harumashi ; and Take-aki Mitsudo
• 刊名：Organometallics
• 出版年：2006
• 出版时间：May 8, 2006
• 年：2006
• 卷：25
• 期：10
• 页码：2547 - 2552
• 全文大小：149K
• 年卷期：v.25,no.10(May 8, 2006)
• ISSN：1520-6041

文摘

The reaction of Ru(⁶-cot)(dmfm)₂ (1; cot = 1,3,5-cyclooctatriene, dmfm = dimethyl fumarate) withwater and dppe derivatives (dppe = 1,2-bis(diphenylphosphino)ethane) having two or four methoxy groupsat the ortho positions of the phenyl rings, (S,S)-DIPAMP or o-MeO-dppe, afforded the unique binuclearRu(II) aqua complexes 4a,b, where two oxaruthenacycles are combined and hold a water molecule bycoordination and hydrogen bonding, as revealed by X-ray crystallography. Although complex 4b has abinuclear form in the solid state, disintegration occurred in solution to give the mononuclear aqua complex4b'. Complex 4b was further treated with ammonia, resulting in the formation of the mononuclear Ru(II)ammonia complex 5 via ligand displacement with water. The water oxygen atom and ammonia nitrogenatom in these complexes can be regarded as chiral centers in the solid state, since they have four differentgroups, distinguished by coordination to ruthenium and nonequivalent hydrogen bondings.