Study of the electronic structure of polynuclear cobalt trimethylacetate complexes by Co3s and Co3p X-ray photoelectron spectroscopy

• Published in: Russian journal of inorganic chemistry 2011, Vol.56 (3), p.402-408
• Main Authors: Kochur, A. G., Ivanova, T. M., Shchukarev, A. V., Linko, R. V., Terebova, N. G., Sidorov, A. A., Eremenko, I. L.
• Format: Article
• Language: English
• Subjects: Approximation; Chemistry; Chemistry and Materials Science; Cobalt; Correlation; Electronic structure; Inorganic Chemistry; Mathematical analysis; Physical Methods of Investigation; Spectra; X-ray photoelectron spectroscopy; X-rays
• ISSN: 0036-0236; 1531-8613; 1531-8613
• DOI: 10.1134/S0036023611030120

The electronic structure of mono-, hexa-, and nonanuclear cobalt trimethylacetate complexes was studied by XPS. The Co3 s - and Co3 p X-ray photoelectron spectra of the complexes were recorded. The Co3 p spectrum of bivalent cobalt was calculated in the isolated-ion intermediate-coupling approximation. Spectrum analysis showed that the [Co( N -Phobsqdi)2(η′- N -Ph-opda)(OOCCMe 3 )] complex is a strong-field complex with Co(III) in the diamagnetic state; the [Co(dipy) 2 (OOCCMe 3 ) 2 ], [Co(dipyam)(OOCCMe 3 ) 2 ], and [Co 9 (μ 3 -OH) 6 (μ-OOCCMe 3 ) 12 (OCMe 2 ) 4 ] are high-spin weak-field Co(II) complexes; and the [Co 6 (μ 4 -O) 2 (OOCCMe 3 ) 10 (THF) 4 ] complex contains both the Co(II) and Co(III) atoms. The energy position of major Co3 s - and Co3 p spectral maxima were found to be sensitive to the nature of the nearest environment of cobalt atoms. The data correlate well with X-ray crystallographic data.