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

The electronic structure of mono-, hexa-, and nonanuclear cobalt trimethylacetate complexes was studied by XPS. The Co3s- and Co3p X-ray photoelectron spectra of the complexes were recorded. The Co3p 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)(OOCCMe3)] complex is a strong-field complex with Co(III) in the diamagnetic state; the [Co(dipy) 2(OOCCMe3)2], [Co(dipyam)(OOCCMe 3)2], and [Co9(μ3-OH) 6(μ-OOCCMe3)12(OCMe2) 4] are high-spin weak-field Co(II) complexes; and the [Co 6(μ4- O)2(OOCCMe3) 10(THF)4] complex contains both the Co(II) and Co(III) atoms. The energy position of major Co3s- and Co3p 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. © Pleiades Publishing, Ltd., 2011