含混合配体的双核Mn(Ⅲ)Schiff碱配合物合成和晶体结构

Syntheses and Crystal Structures of Binuclear Manganese Complexes with Mixed Ligands

合成了含六齿配体1,2-二水杨酰基肼(1,2-disalicyloylhydrazine,DSH)的3种双核Mn(Ⅲ)配合物[Mn_2(DSH)(acac)_2(EtOH)_2]·2H_2O(1),[Mn_2(DSH)(acac)_2(H_2O)_2]·2H_2O(2)和[Mn_2(DSH)(acac)_2-(Py)_2](3)。晶体结构研究表明,1,2-二水杨酰基肼均通过肼基N—N单键桥连2个Mn(Ⅲ)原子,每个Mn(Ⅲ)与配体的2个氧原子、1个氮原子、acac^-的2个氧原子和溶剂的氧/氮原子形成畸变的MnNO_5或MnN_2O_4八面体配位构型。配合物工的晶体通过分子内和分子间氢键作用形成网状结构。配合物2晶体中,O—H……O氢键和若干分子间氧…氧间距在氢键范围,所以可能形成一维的无限链状结构。循环伏安实验表明,配合物1在甲醇溶液中经历了一个不可逆氧化还原反应过程。

Three binuclear Mn(Ⅲ) complexes[Mn_2(DSH) (acac)_2(EtOH)_2]·2H_2O(1), [Mn_2(DSH)-(acac)_2(H_2O)_2]·2H_2O(2) and [Mn_2 (DSH) (acac)_2(py)_2] (3), where DSH(1, 2-disalicyloyl-hydrazine) is the ligand, have been synthesized and characterized by X-ray diffractometry and cyclic voltammetry. Complex 1 crystallizes in triclinic, space group P1, α=1.197 60(6)nm, b=1.208 04(7) nm, c=1.372 98(7) nm, α=89..737(2)°, β=65.900 (4)°, γ=68.752(2)°and Z=2. Complex 2 crystallizes in monoclinic, space group P2_1/n,α=1.196 5(1)nm, b=0.823 17(7)nm, c=1.400 1(1)nm, β=101.035(4)°and Z=2. Complex 3 also crystallizes in monoclinic, space group P2_1/n, α=1.183 11(5)nm, b=0.886 93(5)nm, c=1.655 37(8)nm, β=100.581(4)°and Z=2. In all of the three title complexes, there are centrosymmetrical binuclear manganese complex molecules. Each ligand DSH^(4-) in these complexes bridges the two Mn atoms through its hydrazine N—N group. The manganese atoms in the three complexes have a distorted octahedral geometry.