Titanium, zirconium and hafnium halide complexes of trithioether and triselenoether ligands

Levason, William, Patel, Bhavesh and Reid, Gillian (2004) Titanium, zirconium and hafnium halide complexes of trithioether and triselenoether ligands. Inorganica Chimica Acta, 357 (7), 2115-2120. (doi:10.1016/j.ica.2003.11.042).

Abstract

The reaction of TiX4(X = Cl or Br) with the tripodal ligands MeC(CH2SMe)(3) or MeC(CH2SeMe)(3), (L-3) in anhydrous n-hexane or CH2Cl2 produced the extremely moisture sensitive complexes [TiX4(L-3)]. These were characterised by microanalysis, IR, UV-Vis and variable temperature H-1, C-13{H-1} and Se-77 NMR spectroscopy. The NMR studies showed that in solution in CH2Cl2 the complexes contain L-3 bound as bidentates, and that pyramidal inversion and exchange between the free and coordinated chalcogen donors is rapid at room temperature. Ligand dissociation/exchange increases TiCl4<TiBr4 and MeC(CH2SMe)(3) < MeC(CH2SeMe)(3.) and attempts to isolate TiI4 analogues were unsuccessful. The reactions of [MCl4(Me2S)(2)] (M = Zr or Hf) with (L-3) in anhydrous CH2Cl2 produces white or cream 7-coordinate [MCl4(L-3)], which are insoluble in chlorocarbon solvents. The reactions of TiX4 (X = Cl, Br or I) with the trithia-macrocycles [9]aneS(3) and [10]aneS(3) produced [TiX3([n]aneS(3))]X, whilst reaction of TiCl4. SbCl5 and [9]aneS(3) in anhydrous CH2Cl2 gave [TiCl3([9]aneS(3))]SbCl6. Spectroscopic studies suggest these macrocyclic compounds contain 6-coordinate cations. [TiX3([n]aneS(3))] (n = 9 or 10) but with Zr and Hf the complexes [MCl4([n]aneS(3))] are 7-coordinate and neutral.

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Contributors

Author: William Levason

Author: Gillian Reid

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