新型硫/氧钼配合物(Et_4N)_2[MoO(S_4)(bdtX_2)]和(Et_4N)_2[Mo_2O_2(m_2-S)_2(bdtX_2)]的合成及晶体结构（英文）

Synthesis and Crystal Structures of New Sulfido/oxo-molybdenum Complexes(Et_4N)_2[MoO(S_4)(bdt X_2)] and(Et_4N)_2[Mo_2O_2(μ_2-S)_2(bdtX_2)](X=H and Cl)

在乙腈中,用摩尔比为1∶1的1,2-苯二硫醇(H_2bdt)或3,6-二氯-1,2-苯二硫醇(H_2bdtCl_2)与(Et_4N)_2[MoIVO(S_4)_2]进行取代反应,得到单硫烯钼(IV)氧化合物(Et_4N)_2[MoO(S_4)(bdt X_2)](X=H,1;X=Cl,2)。在热的乙腈中,用摩尔比为1∶1的1,2-芳二硫醇继续与化合物1和2反应,得到双硫桥联的双核钼(V)化合物(Et4N)2[Mo_2O_2(m_2-S)_2(bdt X_2)_2](X=H,3;X=Cl,4)。通过UV-3000紫外分光光度计对这四种配合物进行谱学表征,并采用X射线单晶衍射仪对其中配合物2,3和4的结构进一步测定,结果表明:在化合物3和4结构中,端氧的位置处于Mo_2S_2平面的同侧,为顺式构型。

Substitution of(Et4N)2[MoIVO(S4)2]in acetonitrile with mole ratio(1∶1)1,2-benzenedithiol(H2bdt)and 3,6-dichloro-1,2-benzenedithiol(H2bdtCl2)gave mono(dithiolene)oxo-molybdenum(IV)complexes(Et4N)2[MoO(S4)(bdtX2)](X=H,1;X=Cl,2).Treatment of 1 and 2 with additional equimolar amount of 1,2-arenedithiol in warm acetonitrile afforded bis(μ-sulfido)dimolybdenum(V)species(Et4N)2[Mo2O2(m2-S)2(bdtX2)2](X=H,3;X=Cl,4).All four complexes were characterized spectroscopically with UV-3000 spectrophotometer,of which complexes 2,3 and 4 have been further determined with single-crystal X-ray diffraction.Results show the synisomers are formed referring to the position of the apical oxo ligands with respect to the Mo2S2 plane.