Synthesis, spectroscopic and EXAFS studies of vanadium complexes of trithioether ligands and crystal structures of [VCl3([9]aneS3)] and [VI2(thf)([9]aneS3)] ([9]aneS3 = 1,4,7-trithiacyclononane)

Abstract

A series of vanadium-(II), -(III) and -(IV) macrocyclic thioether complexes has been synthesized and characterised by analytical, magnetic and spectroscopic methods. The new complexes reported are [{V([9]aneS₃)}₂(µ-Cl)₃]Cl ([9]aneS₃ = 1,4,7-trithiacyclononane), [VI₂(thf)([9]aneS₃)], [VI₂(ttob)] (ttob = 2,5,8-trithia[9]-o-benzenophane), [VX₃([9]aneS₃)] (X = Cl, Br or I), [VX₃([10]aneS₃)] ([10]aneS₃ = 1,4,7-trithiacyclodecane), [VCl₃(ttob)], [VCl₃([16]aneS₄)] ([16]aneS₄ = 1,5,9,13-tetrathiacyclohexadecane), [(VX₃)₂(µ-[18]aneS₆)] (X = Cl or Br, [18]aneS₆ = 1,4,7,10,13,16-hexathiacyclooctadecane) and [VOCl₂(ttob)]. The crystal structures of [VI₂(thf)([9]aneS₃)] and [VCl₃([9]aneS₃)] and EXAFS structural data for [VX₃([9]aneS₃)] and [VX₃([10]aneS₃)] are presented and discussed. The acyclic trithioether complexes [VX₃{MeC(CH₂SMe)₃}] (X = Cl or Br) and the complex [VI₂(py)₄] are also reported.