CoII Complexes with Mixed Amino-N and Thiolato-S Donor Sets − Structural Characterization and Electronic Properties of a Stable Bis(μ-thiolato)-Bridged Binuclear CoII Complex
✍ Scribed by Didier Bonnet; Philippe Leduc; Eckhard Bill; Geneviève Chottard; Daniel Mansuy; Isabelle Artaud
- Publisher
- John Wiley and Sons
- Year
- 2001
- Tongue
- English
- Weight
- 418 KB
- Volume
- 2001
- Category
- Article
- ISSN
- 1434-1948
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✦ Synopsis
Two different ligands [S 2 N 3 py ] and [S 2 N 2 ], prepared from 2,6bis [1-(2-mercaptoanilino)ethyl]pyridine and 2,3-bis(2-mercaptoanilino)butane, respectively, have been used to investigate cobalt coordination with mixed amine nitrogen/sulfur donor sets. The pentadentate [S 2 N 3 py ] ligand gave rise to a mononuclear [Co II (S 2 N 3 py )] complex, which was found to be stable only at low temperatures under argon, and was characterized as having a high-spin Co II state on the basis of 1 H NMR and EPR measurements. In contrast, the tetradentate [S 2 N 2 ] ligand led to a binuclear bis(µ-thiolato) [Co II (S 2 N 2 )] 2 complex, the structure of which was solved by X-ray crystallography. Each Co II centre was found to reside in an N 2 S 3 square-pyramidal environment in the crystal, the two Co atoms being bridged by one of the two thiolates of an [S 2 N 2 ] ligand. On the basis of the temperature dependence of the magnetic susceptibility, the two Co II centres were found to be in a low-spin state and slightly antiferromagnetically coupled with an absolute J value of less than 3 cm -1 . In aerated