Heterobimetallic Mn/Co hybrid complexes composed of proximate organometallic and classical coordination sites

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• 作者：Huaxin Zhang ; Sebastian Dechert ; Jö ; rg Maurer ; Michael Linseis ; Rainer F. Winter ; Franc Meyer
• 关键词：Bridging ligands ; N-functionalized cyclopentadienyl ligands ; Manganese ; Cobalt ; Bimetallic complexes
• 刊名：Journal of Organometallic Chemistry
• 出版年：2007
• 期刊代码：64_0022328x
• 类别：ch
• 出版时间：15 June 2007
• 卷：692
• 期：14
• 页码：2956-2964
• 文件大小：624 K

摘要

A series of highly unsymmetric heterobinuclear Mn/Co complexes is reported, in which an organometallic CpMn(CO)₂ fragment and a classical Werner-type cobalt(II) subunit are arranged in close proximity by means of a bridging pyrazolate. Two ligand scaffolds are employed that differ by the chelate size of the tripodal tetradentate {N4} binding site for cobalt. Molecular structures of three complexes with either nitrate or acetate coligands have been characterized by X-ray crystallography. IR and UV–Vis-spectroelectrochemistry reveals that oxidation of the heterobimetallic systems is highly localized at the organometallic manganese site, while electrochemical reduction occurs at cobalt. Structural and spectroscopic features as well as trends for the redox potentials of the Mn^I/Mn^II couple suggest that changes at the cobalt(II) Werner-type subunit have only minor effects on the properties of the organometallic site.