Investigation of electronic structure of tri- and tetranuclear molybdenum clusters by X-ray photoelectron and emission spectroscopies and quantum chemical methods

Investigation of electronic structure of tri- and tetranuclear molybdenum clusters by X-ray photoelectron and emission spectroscopies and quantum chemical methods Full article

Journal

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
ISSN: 1386-1425 , E-ISSN: 1873-3557

Output data

Year: 2018, Volume: 190, Pages: 347-352 Pages count : 6 DOI: 10.1016/j.saa.2017.09.043

Tags

Sulfide cluster, Molybdenum, Thiourea, Bipyridine, X-ray photoelectron spectroscopy, X-ray emission spectroscopy, Quantum chemical calculations, DFT method

Authors

Kryuchkova N.A. ^1,2 , Syrokvashin M.M. ¹ , Gushchin A.L. ^1,2 , Korotaev E.V. ¹ , Kalinkin A.V. ³ , Laricheva Yu.A. ¹ , Sokolov M.N. ^1,2,4

Affiliations

1	Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Lavrentyev Av., 3, RU-630090 Novosibirsk, Russia
2	Novosibirsk State University, Pirogova St., 2, RU-630090 Novosibirsk, Russia
3	Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Lavrentyev Av., 5, RU -630090 Novosibirsk, Russia
4	Kazan Federal University, Kremlyovskaya St., 18, Kazan 420008, Russia

Charge state studies of compounds [Mo3S4(tu)8(H2O)]Cl4·4H2O (1), [Mo3S4Cl3(dbbpy)3]Cl·5H2O (2), [Mo3S4(CuCl)Cl3(dbbpy)3][CuCl2] (3), containing {Mo3S4}4+ and {Mo3CuS4}5+ 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 {Mo3S4} in 3 does not lead to significant changes in the charge state of the molybdenum atoms and the {Mo3S4} unit can be considered as a tridentate metallothia crown ether.

Kryuchkova N.A. , Syrokvashin M.M. , Gushchin A.L. , Korotaev E.V. , Kalinkin A.V. , Laricheva Y.A. , Sokolov M.N.
Investigation of electronic structure of tri- and tetranuclear molybdenum clusters by X-ray photoelectron and emission spectroscopies and quantum chemical methods
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 2018. V.190. P.347-352. DOI: 10.1016/j.saa.2017.09.043 Scopus OpenAlex

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