Electron-transfer-catalyzed ligand substitution of carboxylato niobocene complex induced by electrochemical oxidation
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文摘
Electrochemical reduction of niobocene dichloride (??5-C5H4SiMe3)2NbCl2 1 formulated as Formula Not Shown in the presence of 3,4-diaminobenzoic acid yields to the complex [Nb(??5-C5H4SiMe3)2(??2-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(??5-C5H4SiMe3)2(??1-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.
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