Crystal Structure and X-ray Crystallographic Analysis of the Binuclear Cluster Thiocyanate Complex of Niobium(IV) Full article
| Journal |
Journal of Structural Chemistry
ISSN: 0022-4766 , E-ISSN: 1573-8779 |
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| Output data | Year: 2021, Volume: 62, Number: 10, Pages: 1531-1542 Pages count : 12 DOI: 10.1134/S0022476621100073 | ||||||||
| Tags | sulfide clusters, niobium, rhodanide, single crystal XRD, XPS, X-ray electron spectroscopy, XANES, electronic structure | ||||||||
| Authors |
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| Affiliations |
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Funding (2)
| 1 | The Ministry of Education and Science of the Russian Federation | FWUZ-2021-0002 (121031700315-2) |
| 2 | Ministry of Science and Higher Education of the Russian Federation | FWUZ-2021-0006 (121031700314-5) |
Abstract:
The structure of a binuclear niobium(IV) thiocyanate complex (Bu4N)4[Nb2(μ2-S2)2(NCS)8]·H2O (1·H2O) is studied by X-ray crystallography. Compound 1·H2O crystallizes in the orthorhombic crystal system (space group Pbca) with unit cell parameters a = 23.2139(4) Å, b = 25.2962(4) Å,
с = 32.5478(6) Å, V = 19112.8(6) Å3, R = 0.0592. The electronic structures of (Bu4N)4[Nb2(μ2-S2)2(NCS)8] and (Bu4N)4[Nb2(μ2-Se2)2(NCS)8] complexes are investigated by X-ray spectroscopy techniques and compared with the structures of polymeric chalcogenides Nb2S4Br4 and Nb2Se4Br4. By XPS it is shown that effective charges on atoms of the {Nb2(μ-Q2)2}4+ (Q = S, Se) core do not change when passing from Br– to NCS– ligands. The HOMO and LUMO structures of (Bu4N)4[Nb2(μ2-S2)2(NCS)8] and (Bu4N)4[Nb2(μ2-Se2)2(NCS)8] are analyzed by XPS and XANES techniques. The largest contributions of S 3p states of NCS– ligands to the occupied molecular orbitals are found to be near the upper boundary of the valence band while the contributions from dichalcogenide bridging ligands have a more uniform distribution. For the conduction band, the contributions of S 3p states of NCS– ligands are located deeper whereas the contributions from dichalcogenide bridging ligands are near the lower boundary of the conduction band. The interaction of Nb 4d and S 3p/Se 4p states of dichalcogenide bridges for the HOMO has an antibonding character, which is bonding for all the other occupied molecular orbitals and antibonding for all unoccupied molecular orbitals.
Cite:
Fedorenko A.D.
, Fomenko I.S.
, Gongola M.I.
, Pervukhina N.V.
, Kalinkin A.V.
, Nikolenko A.D.
, Gushchin A.L.
Crystal Structure and X-ray Crystallographic Analysis of the Binuclear Cluster Thiocyanate Complex of Niobium(IV)
Journal of Structural Chemistry. 2021. V.62. N10. P.1531-1542. DOI: 10.1134/S0022476621100073 WOS Scopus РИНЦ AN OpenAlex
Crystal Structure and X-ray Crystallographic Analysis of the Binuclear Cluster Thiocyanate Complex of Niobium(IV)
Journal of Structural Chemistry. 2021. V.62. N10. P.1531-1542. DOI: 10.1134/S0022476621100073 WOS Scopus РИНЦ AN OpenAlex
Original:
Федоренко А.Д.
, Фоменко Я.С.
, Гонгола М.И.
, Первухина Н.В.
, Калинкин А.В.
, Николенко А.Д.
, Гущин А.Л.
Кристаллическая структура и рентгеноспектральное исследование биядерного тиоцианатного кластерного комплекса ниобия(IV)
Журнал структурной химии. 2021. Т.62. №10. С.1636-1647. DOI: 10.26902/jsc_id80811 РИНЦ OpenAlex
Кристаллическая структура и рентгеноспектральное исследование биядерного тиоцианатного кластерного комплекса ниобия(IV)
Журнал структурной химии. 2021. Т.62. №10. С.1636-1647. DOI: 10.26902/jsc_id80811 РИНЦ OpenAlex
Dates:
| Submitted: | Apr 14, 2021 |
| Accepted: | May 26, 2021 |
| Published print: | Oct 1, 2021 |
| Published online: | Nov 16, 2021 |
Identifiers:
| Web of science: | WOS:000719338400007 |
| Scopus: | 2-s2.0-85119137113 |
| Elibrary: | 47528061 |
| Chemical Abstracts: | 2021:2500504 |
| OpenAlex: | W3212841775 |