SYNTHESIS, SPECTROSCOPIC AND EXAFS STUDIES OF VANADIUM COMPLEXES OF TRITHIOETHER LIGANDS AND CRYSTAL-STRUCTURES OF [VCL3([9]ANES(3))] AND [VI2(THF)([9]ANES(3))] ([9]ANES(3) = 1,4,7-TRITHIACYCLONONANE)

A series of vanadium-(II), -(III) and -(Iv) macrocyclic thioether comp lexes has been synthesized and characterised by analytical, magnetic a nd spectroscopic methods. The new complexes reported are [{V([9]aneS(3 ))}(2)(mu-Cl)(3)]Cl ([9]aneS(3) = 1,4,7-trithiacyclononane), [VI2(thf) ([9]aneS(3))], [VI2(ttob)] (ttob = 2,5,8-trithia[9]-o-benzenophane), [ VX3([9]aneS(3))] (X = Cl, Br or I), [VX3([10]aneS(3))] ([10]aneS(3) = 1,4,7-trithiacyclodecane), [VCl3(ttob)], [VCl3([16]aneS(4))] ([16]aneS (4) = 1,5,9,13-tetrathiacyclohexadecane), [(VX3)(2)(mu-[18]aneS(6))] ( X = Cl or Br [18]aneS(6) = 1,4,7,10,13,16-hexathiacyclooctadecane) and [VOCl2(ttob)]. The crystal structures of [VI2(thf)([9]aneS(3))] and [ VCl3([9]aneS(3))] and EXAFS structural data for [VX3([9]aneS(3))] and [VX3([10]aneS(3))] are presented and discussed. The acyclic trithioeth er complexes [VX3{MeC(CH2SMe)(3)}] (X = Cl or Br) and the complex [VI2 (py)(4)] are also reported.