Crystal Structure and X-ray Crystallographic Analysis of the Binuclear Cluster Thiocyanate Complex of Niobium(IV) | Sciact - CRIS-система Института катализа

Crystal Structure and X-ray Crystallographic Analysis of the Binuclear Cluster Thiocyanate Complex of Niobium(IV) Научная публикация

Журнал

Journal of Structural Chemistry
ISSN: 0022-4766 , E-ISSN: 1573-8779

Вых. Данные

Год: 2021, Том: 62, Номер: 10, Страницы: 1531-1542 Страниц : 12 DOI: 10.1134/S0022476621100073

Ключевые слова

sulfide clusters, niobium, rhodanide, single crystal XRD, XPS, X-ray electron spectroscopy, XANES, electronic structure

Авторы

Fedorenko A.D. ¹ , Fomenko I.S. ¹ , Gongola M.I. ² , Pervukhina N.V. ¹ , Kalinkin A.V. ³ , Nikolenko A.D. ^3,4 , Gushchin A.L. ¹

Организации

1	Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2	Novosibirsk State University, Novosibirsk, Russia
3	Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
4	Budker Institute of Nuclear Physics, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia

Информация о финансировании (2)

1	Министерство образования и науки Российской Федерации	FWUZ-2021-0002 (121031700315-2)
2	Министерство науки и высшего образования Российской Федерации (с 15 мая 2018)	FWUZ-2021-0006 (121031700314-5)

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.

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 CAPlus OpenAlex

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

Поступила в редакцию:	14 апр. 2021 г.
Принята к публикации:	26 мая 2021 г.
Опубликована в печати:	1 окт. 2021 г.
Опубликована online:	16 нояб. 2021 г.

Web of science:	WOS:000719338400007
Scopus:	2-s2.0-85119137113
РИНЦ:	47528061
Chemical Abstracts:	2021:2500504
OpenAlex:	W3212841775

БД	Цитирований
Scopus	2
Web of science	1
РИНЦ	4
OpenAlex	2