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

The preparation of an unsymmetrical binucleating ligand bearing a bridging oxadiazole ring flanked on one side by three ligands and on the other by four ligands is described. When bound to two metals, the ligand forms complexes where the metals are in 5- and 6-coordinate sites after the incorporatio...

Full description

Saved in:
Bibliographic Details
Published in:Inorganic chemistry 2001-08, Vol.40 (17), p.4101-4108
Main Authors: Incarvito, Christopher, Rheingold, Arnold L, Gavrilova, Anna L, Qin, C. Jin, Bosnich, B
Format: Article
Language:English
Subjects:
Binding Sites
Cobalt - chemistry
Ligands
Oxidation-Reduction
Spectrum Analysis
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The preparation of an unsymmetrical binucleating ligand bearing a bridging oxadiazole ring flanked on one side by three ligands and on the other by four ligands is described. When bound to two metals, the ligand forms complexes where the metals are in 5- and 6-coordinate sites after the incorporation of an exogenous bridging ligand. A di-Co2+ complex of this ligand has been prepared containing a hydroxide bridge. The complex is readily oxidized 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. The ligand 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.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic010235r