The synthesis and crystal structure of the molecular complexes trans-[TiIVX4(OPPh3)2] (X = Cl, Br, I)

• Published in: Inorganica Chimica Acta 2025-01, Vol.574, p.122356, Article 122356
• Main Authors: Krupenko, N.R., Poltarak, P.A., Artemkina, S.B., Grayfer, E.D., Brylev, K.A.
• Format: Article
• Language: English
• Subjects: Bromide; Chloride; Crystal structure; Iodide; Magnetically diluted systems; Molecular complex; Synthesis; Titanium; Triphenylphosphine oxide
• ISSN: 0020-1693
• DOI: 10.1016/j.ica.2024.122356

[Display omitted] •A series of molecular complexes trans-[TiX4(OPPh3)2] (X = Cl, Br, I) were synthesized by heating of the TiX4 and OPPh3.•The method for the synthesis of TiCl4 from AgCl and Ti powder in preparative quantities has been proposed.•Geometric parameter analysis showed trans-[MX4(OPPh3)2] geometry independence from different central atoms (M=Ti, Nb, Re). The series of titanium (IV) complexes trans-[TiCl4(OPPh3)2] (1), trans-[TiBr4(OPPh3)2] (2) and trans-[TiI4(OPPh3)2] (3) were obtained as polycrystalline powders by heating the corresponding metal tetrahalides with triphenylphosphine oxide in evacuated sealed glass ampoules. The crystal structures were determined by single crystal X-ray diffraction. Compounds 1 and 2 were isolated as yellow and brown crystalline powders, with yields 70 and 75%, respectively. This paper discusses the synthesis of these coordination compounds 1–3 and their crystal structures, and analyzes the geometric parameters of the related molecular complexes of niobium and rhenium for use in the design of magnetically diluted systems.