Unusual structural variations within a family of thioether macrocyclic complexes. Tin(IV) halide adducts of [12]-, [14]- and [16]-aneS(4)

Levason, William, Matthews, Melissa L., Patel, Rina, Reid, Gillian and Webster, Michael (2003) Unusual structural variations within a family of thioether macrocyclic complexes. Tin(IV) halide adducts of [12]-, [14]- and [16]-aneS(4). New Journal of Chemistry, 27 (12), 1784-1788. (doi:10.1039/b307863a).

Abstract

The hydrolytically sensitive compounds [(SnCl4)(2)([n]aneS(4))] (n = 12, 14, 16) and [SnBr4([n]aneS(4))] are obtained in good yield upon reaction of 2 mol. equiv. of the parent tin tetrahalide with 1 mol. equiv. of macrocycle in rigorously anhydrous CH2Cl2 solution. Reactions of [16]aneSe(4) with SnX4 (X = Cl or Br) affords [SnX4([16]aneSe(4))], while reaction of [8]aneSe(2) gives [SnCl4([8]aneSe(2))]. The crystal structures of the three closely related complexes [SnBr4([12]aneS(4))], [SnBr4([14]aneS(4))].2/3CH(2)Cl(2) and [SnBr4([16]aneS(4))] have been determined. These species represent the first examples of Sn(IV) halide adducts with neutral Group 16 ligands which adopt polymeric structures. The complexes are all chain polymers, although there is unexpected structural dependence upon the macrocycle ring-size, giving each a distinct structural form. Unusually, the coordinated S atoms in both [SnBr4([14]aneS(4))].2/3CH(2)Cl(2) and [SnBr4([16]aneS(4))] adopt a mutually trans arrangement. Far-IR spectra indicate that the chloro complexes all exist as cis octahedral tin(IV) species. Solution NMR spectroscopy shows that the tetrathia and tetraselena macrocyclic complexes are extensively dissociated at 295 K.

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Contributors

Author: William Levason

Author: Gillian Reid

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