Synthesis and Theoretical Studies of the Stability of Tetrahalide Tungsten Molecular Complexes trans-[WX4(OPPh3)2] (X = Cl, Br, or I)

Synthesis and Theoretical Studies of the Stability of Tetrahalide Tungsten Molecular Complexes trans-[WX4(OPPh3)2] (X = Cl, Br, or I) Научная публикация

Журнал

Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X

Вых. Данные

Год: 2025, Том: 64, Номер: 51, Страницы: 25053–25064 Страниц : 12 DOI: 10.1021/acs.inorgchem.5c03260

Авторы

Krupenko N.R. ¹ , Poltarak P.A. ¹ , Artemkina S.B. ¹ , Lavrov A.N. ¹ , Gabrienko A.A. ² , Brylev K.A. ¹

Организации

1	Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Novosibirsk 630090, Russian Federation
2	Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Novosibirsk 630090, Russian Federation

The work is devoted to theoretical and experimental study of synthesis and stability of tungsten tetrahalide complexes [WX4(OPPh3)2] (X=Cl, Br, I). New molecular complexes of tungsten (IV) trans-[WCl4(OPPh3)2] (1) and trans-[WBr4(OPPh3)2] (2) were obtained in the form of polycrystalline powders, starting from different tungsten sources: oxotetrahalides, hexahalides or trioxide, in the presence of triphenylphosphine and triphenylphosphine oxide. The X-ray crystal structures were determined for 1 and 2 (1: P-1, a = 9.3841(10) Å, b = 9.6332(10) Å, c = 10.4243(13) Å, α = 101.585(4)°, β = 108.097(4)°, γ = 93.365(4)°, Z = 1, V = 870.03(17) Å3; 2: P21, a = 10.0217(14) Å, b = 15.380(3) Å, c = 11.9399(19) Å, β = 100.805(5)°, Z = 2, V = 1807.7(5) Å3). Magnetic susceptibility measurements revealed Van Vleck paramagnetism for the both compounds. In order to estimate the enthalpy of the studied reactions and predict the existence of trans-[WI4(OPPh3)2], DFT calculations were performed. The article discusses the synthesis of new complex compounds 1, 2, their crystal structures, magnetic properties and results of DFT calculations for reactions of obtaining [WX4(OPPh3)2] (X = Cl, Br, I).

Krupenko N.R. , Poltarak P.A. , Artemkina S.B. , Lavrov A.N. , Gabrienko A.A. , Brylev K.A.
Synthesis and Theoretical Studies of the Stability of Tetrahalide Tungsten Molecular Complexes trans-[WX4(OPPh3)2] (X = Cl, Br, or I)
Inorganic Chemistry. 2025. V.64. N51. P.25053–25064. DOI: 10.1021/acs.inorgchem.5c03260

Поступила в редакцию:	16 июл. 2025 г.
Принята к публикации:	4 дек. 2025 г.
Опубликована online:	12 дек. 2025 г.
Опубликована в печати:	29 дек. 2025 г.

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