摘要
Tris[o-mercaptophenolato]vanadium(IV)dimer complexes(A)_2[V(mp)_3NaLL']_2(A= Ph_4P^+,H_2mp=o-mercaptophenol,L=MeCN,L'=EtOH,(1);L'=MeOH,(2))were prepared by the reaction of anhydrous VCl_3 and Na_2mp in the molar ratio 1:3.Complex(3)(A=Et,N^+,L=L'= MeOH)was prepared by the reaction of VCl_3,Na_2mp and Li_2S in the molar ratio 1:2:1.The com- plexes were characterized by X-ray diffraction crystallography,infrared spectra,magnetic suseepti- bility,and cyclic voltammetric measurements.Complex 2 crystallizes in the triclinic space group P1 with a=12.813(6),b=14.199(4),c=12.790(5),α=112.72(2),β=104.24(4).γ=88.68(4)°,V= 2073.6,and Z=1.The structure was refined to R=0.058.Complex 3 crystallizes in the mono- clinic space group P2_1/n with a=12.359(3),b=17.452(6),c=14.829(13),β=96.51(5)°,V=3177.8, and Z=2.The final R factor is 0.067.Both of the anions of 2 and 3 contain two[V(rap)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.
Tris[o-mercaptophenolato]vanadium(IV)dimer complexes(A)_2[V(mp)_3NaLL']_2(A= Ph_4P^+,H_2mp=o-mercaptophenol,L=MeCN,L'=EtOH,(1);L'=MeOH,(2))were prepared by the reaction of anhydrous VCl_3 and Na_2mp in the molar ratio 1:3.Complex(3)(A=Et,N^+,L=L'= MeOH)was prepared by the reaction of VCl_3,Na_2mp and Li_2S in the molar ratio 1:2:1.The com- plexes were characterized by X-ray diffraction crystallography,infrared spectra,magnetic suseepti- bility,and cyclic voltammetric measurements.Complex 2 crystallizes in the triclinic space group P1 with a=12.813(6),b=14.199(4),c=12.790(5),α=112.72(2),β=104.24(4).γ=88.68(4)°,V= 2073.6,and Z=1.The structure was refined to R=0.058.Complex 3 crystallizes in the mono- clinic space group P2_1/n with a=12.359(3),b=17.452(6),c=14.829(13),β=96.51(5)°,V=3177.8, and Z=2.The final R factor is 0.067.Both of the anions of 2 and 3 contain two[V(rap)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.
基金
Project supported by the National Natural Science Foundation of China,the Natural Science Foundation of Chinese Academy of Sciences and the Natural Science Foundation of Fujian
