Bimetallic Reactivity. One-site Addition Two-metal Oxidation Reactions Using a Di-Co(II) Complex of a Binucleating Ligand with 5- and 6-Coordinate Sites

详细信息    查看全文

• 作者：Christopher Incarvito ; Arnold L. Rheingold ; Anna L. Gavrilova ; C. Jin Qin ; and B. Bosnich
• 刊名：Inorganic Chemistry
• 出版年：2001
• 出版时间：August 13, 2001
• 年：2001
• 卷：40
• 期：17
• 页码：4101 - 4108
• 全文大小：121K
• 年卷期：v.40,no.17(August 13, 2001)
• ISSN：1520-510X

文摘

The preparation of an unsymmetrical binucleating ligand bearing a bridging oxadiazole ring flanked on one sideby three ligands and on the other by four ligands is described. When bound to two metals, the ligand formscomplexes where the metals are in 5- and 6-coordinate sites after the incorporation of an exogenous bridgingligand. A di-Co²⁺ complex of this ligand has been prepared containing a hydroxide bridge. The complex is readilyoxidized to the di-Co³⁺ state by outer sphere electron transfer with ferrocenium ions. Addition of Br₂ or NO₂⁺to the di-Co²⁺ complex leads to the rapid formation of the di-Co³⁺ bromo or nitro complexes, respectively. Theligand characteristics which allow for double oxidation with ferrocenium ions and for the one-site addition two-metal oxidations with Br₂ and NO₂⁺ are discussed in terms of mechanical coupling between the two metal sites.