两个N,N′-亚乙基双(1-苯基-3-亚氨基-1-丁酮)锰(Ⅲ)配合物的合成、表征和晶体结构

Syntheses, Characterization and Crystal Structure of Two Manganese(Ⅲ) Complexes with Ligand N,N′-Ethylenebis(1-phenyl-3-imino-1-butanone)

合成了两个 N,N′-亚乙基双 ( 1 -苯基 -3 -亚氨基 -1 -丁酮 ) (简写为 H2 bzacen)的锰配合物 Mn( bzacen)·( NO2 ) ( Et OH) ( 1 )和 Mn( bzacen) ( NO2 ) ( Me OH) ( 2 ) .晶体结构分析表明 :配合物 1晶体属正交晶系 ,空间群 Pbca,晶胞参数 a=2 .81 73 ( 6) nm,b=2 .1 94 6( 4) nm,c=0 .7683 ( 6) nm,V=4 .750 ( 5) nm3 ,Z=8,μ=5.71 cm-1,R=0 .0 540 .配合物 2晶体属正交晶系 ,空间群 Pbca,晶胞参数 a=2 .764 1 ( 6) nm,b=2 .1 83 2 ( 4) nm,c=0 .770 5( 2 ) nm,V=4 .650 ( 3 ) nm3 ,Z=8,μ=5.81 cm-1,R=0 .0 564 .在这两个配合物中 ,Mn( )原子均具有畸变的 N2 O4 八面体配位构型 ,整个晶体通过分子间氢键作用形成一维的无限链状结构 .红外光谱表明 ,配体在形成配合物后 ,νC=N,νC=O和νC=C谱带移向低频 ,NO-2 以一个 O原子与 Mn( )配位 .电子光谱表明存在 d-d* ,π-π*和

Two manganese(Ⅲ) complexes with the ligand bzacen 2- [bzacen 2- = N, N ′ ethylenebis(1 phenyl 3 imino 1 butanone)], Mn(bzacen)(NO 2)(EtOH) (1) and Mn(bzacen)(NO 2)(MeOH) (2), have been synthesized and characterized by IR, electronic spectra and cyclic voltammetry. Both complexes crystallize in the orthorhombic system, space group Pbca , with parameters for complex 1: a =2.817 3(6) nm, b =2.194 6(4) nm, c =0.768 3(6) nm, V =4.750(5) nm 3, Z =8, μ =5.71 cm -1 , and with parameters for complex 2: a =2.764 1(6) nm, b =2.183 2(4) nm, c =0.770 5(2) nm, V =4.650(3) nm 3, Z =8, μ =5.81 cm -1 . The final R values are 0.054 0 for complex 1 and 0.056 4 for complex 2, respectively. The structure determination of the title complexes reveals an octahedral coordination with an N 2O 2 equatorial plane composed of the donor atoms from the Schiff base ligand bzacen 2- . In these complexes, ν C=N , ν C=O and ν C=C are shifted to lower frequencies in IR spectra; π π * transitions, d π * charge transitions and d d * ligand field transitions are observed in their electronic spectra.