Abstract: 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).

Cite: 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

Dates:

Submitted:	Jul 16, 2025
Accepted:	Dec 4, 2025
Published online:	Dec 12, 2025
Published print:	Dec 29, 2025

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