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Electron-transfer-catalyzed ligand substitution of carboxylato niobocene complex induced by electrochemical oxidation
Authors:Laurent Salvi  Hélène Cattey  Yves Mugnier  Antonio Otero
Abstract:Electrochemical reduction of niobocene dichloride (η5-C5H4SiMe3)2NbCl21 formulated as View the MathML source in the presence of 3,4-diaminobenzoic acid yields to the complex Nb(η5-C5H4SiMe3)22-O,O-OOC(C6H3)(NH2)2)] 3. When CN(2,6-Me2C6H3) formulated as xylylisonitrile (CNXylyl) is added to a complex 3 solution, a substitution reaction takes place to lead to the complex Nb(η5-C5H4SiMe3)21-O-OOC(C6H3)(NH2)2)(CN(2,6-Me2C6H3)) 4 after 3 h. An alternative way to yield quantitatively and nearly instantaneously 4 consists in a previous oxidation of 3 in the presence of CNXylyl. Hence, we present here a new example of electron-transfer-catalyzed (ETC) ligand substitution of carboxylato niobocene complex induced by electrochemical oxidation. The structure of the complexes, the formation mechanism are described using electrochemical and spectroscopic data. Electrochemical simulation have been done to verify experimental results and to complete them with a kinetic study.
Keywords:Niobocene  Electrochemistry  Carboxylato ligand  Isonitrile  Electron-transfer-catalyzed ligand substitution  Synthesis
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