Vanadium(IV) dimer complexes containing [V( o ‐C 6 H 4 OS) 3 ] 2− fragment and caged sodium ions

Tris[ o ‐mercaptophenolato]vanadium(IV) dimer complexes (A) 2 [V(mp) 3 NaLL'] 2 (A = Ph 4 P + , H 2 mp = o ‐mercaptophenol, L = MeCN, L'=EtOH, (1); L' = MeOH, (2)) were prepared by the reaction of anhydrous VC1 3 , and Na 2 mp in the molar ratio 1:3. Complex (3) (A = Et 4 N + , L=L' = MeOH) was prepared by the reaction of VC1 3 , Na 2 mp and Li 2 S in the molar ratio 1:2:1. The complexes were characterized by X‐ray diffraction crystallography, infrared spectra, magnetic susceptibility, and cyclic voltammetric measurements. Complex 2 crystallizes in the triclinic space group P 1 with a =12.813(6), b = 14.199(4), c = 12.790(5) Å, α = 112.72(2), β = 104.24(4). γ = 88.68(4)°, V = 2073.6 Å 3 , and Z =1. The structure was refined to R =0.058. Complex 3 crystallizes in the mono‐clinic space group P 2 1 / n with a =12.359(3), b =17.452(6), c =14.829(13) Å, βequals;96.51(5)°, V =3177.8 Å 3 , and Z =2. The final R factor is 0.067. Both of the anions of 2 and 3 contain two [V(mp) 3 ] 2− fragments linked by sodium ions through the μ 3 ‐O bridges with a crystallographic center of symmetry. The V(IV) atom is in a coordination environment intermediate between a trigonal prism and an ideal octahedron.