Titanium(IV) iodide complexes with phosphine and arsine donor ligands and the crystal structures of the iron(II)/(III) redox pair FeI2{o-C6H4(AsMe2)(2)}(2) (0/+)

Levason, W., Matthews, M. L., Patel, B., Reid, G. and Webster, M. (2004) Titanium(IV) iodide complexes with phosphine and arsine donor ligands and the crystal structures of the iron(II)/(III) redox pair FeI2{o-C6H4(AsMe2)(2)}(2) (0/+). Polyhedron, 23 (4), 605-609. (doi:10.1016/j.poly.2003.10.010).

Abstract

Red-brown [TiI4{o-C6H4(PMe2)(2)}] and [TiI4{o-C6H4(AsMe2)(2)}] have been prepared from the ligands and TiI4 in a 1:1 molar ratio in anhydrous CH2Cl2. They have been characterised by analysis, IR, H-1 and P-31{H-1} NMR and UV-Visible spectroscopy as appropriate and have six-coordinate (cis) octahedral geometries. Investigation of the yellow or fawn products from reactions of TiI4 and the ligands in a 1:2 molar ratio, and suggested in the literature to be bis(ligand)-Ti(IV) complexes, have shown that these are mixtures containing iodinated and oxidised ligands, but do not contain Ti(IV)-iodide complexes. The crystal structures of two iron-diarsine complexes [FeI2{o-C6H4(AsMe2)(2)}(2)] and [FeI2{o-C6H4(AsMe2)(2)}(2)]I-3 . 2CH(2)Cl(2) arising from iron iodide impurities in one commercial sample of TiI4 are reported. The complexes constitute a redox pair and the iron(III) complex is the first pseudo-octahedral iron(III) iodide complex to be structurally characterised.

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Contributors

Author: W. Levason

Author: G. Reid

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