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Investigation of electronic structure of tri- and tetranuclear molybdenum clusters by X-ray photoelectron and emission spectroscopies and quantum chemical methods. | LitMetric
Charge state studies of compounds [MoS(tu)(HO)]Cl·4HO (1), [MoSCl(dbbpy)]Cl·5HO (2), [MoS(CuCl)Cl(dbbpy)][CuCl] (3), containing {MoS} and {MoCuS} cluster cores bearing terminal thiourea (tu) or 4,4'-di-tert-butyl-2,2'-bipyridine (dbbpy) ligands, have been performed by X-ray photoelectron and X-ray emission spectroscopies combined with quantum chemical calculations. The best agreement between theory and experiments has been obtained using the B3LYP method. According to the experimental and calculated data, the Mo atoms are in the oxidation state 4+ for all compounds. The energies and shapes of the Cu2p lines indicate formal oxidation states of Cu as 1+. The coordination of Сu(I) to the cluster {MoS} in 3 does not lead to significant changes in the charge state of the molybdenum atoms and the {MoS} unit can be considered as a tridentate metallothia crown ether.
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