{[Mn(μ-maleate)(phen)(H_2O)_2]·2H_2O}_n的合成及其性质  

Synthesis, Crystal Structure, IR Spectrum and Thermochemical Study of {[Mn(μ-maleate)(phen)(H_2O) 2]·2H_2O}_n

作　　者：张存根[1] 周锦鑫[1] 刘兵 马紫峰[1] 

机构地区：[1]上海交通大学化学化工学院,上海200240

出　　处：《上海交通大学学报》2000年第4期550-553,557,共5页Journal of Shanghai Jiaotong University

基　　金：上海交通大学科技基金;上海市教委科技发展基金! ( 98JG0 5 0 42 )

摘　　要：报道了一个新型一维的多核锰的配合物 {[Mn( μ- maleate) ( phen) ( H2 O) 2 ]· 2 H2 O}n( I)( phen为邻菲罗啉 ,μ- maleate为马来酸根桥 )的合成、元素分析、晶体结构、红外光谱和热重分析 .( I)是通过马来酸锰与邻菲罗啉在乙醇的水溶液中制得的 .其晶体属于三斜晶系 ,空间群为 P- 1 ,a=0 .81 1 9( 1 )、b=0 .81 57( 1 )、c=1 .3632 ( 1 ) nm、α=99.0 8( 1 )、β=87.1 1 ( 1 )、γ=1 0 1 .94°、V=0 .872 1 ( 3) nm3 、Z=2、Dc=1 .60 4 g/cm3 、μ=7.73cm-1、F( 0 0 0 ) =434.结构解析采用直接法 ,R和 Rw 分别收敛到 0 .0 37和 0 .0 50 .单晶结构分析表明 ,( I)中 Mn原子是六配位的 ,配位原子分别为邻菲罗啉的两个 N原子、两个 H2 O中的 O原子和两个马来酸根的 O原子 .马来酸根配体通过两端的羧基氧与 Mn原子桥联进而形成一条无穷链 .配合物分子中存在两种氢键 :即一个未配位的羧酸氧原子与一个已配位的 H2 O分子间形成的分子内氢键 ;结晶水分子与配合物链上的 O原子及配位水分子间的分子间氢键 .红外光谱对羧基在 1 42 5、1 540 cm-1处的对称和不对称伸缩振动以及配位水分子和晶格水分子在 350 0～ 31 0 0 cm-1处的振动吸收进行了归属 .热重分析表明 ,晶体约在 60°C开始失去结晶水 。A novel one dimensional polymeric manganese complex, {[Mn( μ maleate)(phen)(H 2O) 2]·2H 2O} n (I) was synthesized and characterized by elemental analysis and crystal structure diffraction. The IR absorption peaks were assigned and the thermochemical property was studied. (I) was prepared by the reaction of manganese(Ⅱ) maleate with phen in an aqueous solution containing the same volume of EtOH. It crystallizes in triclinic, space group P 1, with a=0.811 9(1), b=0.815 7(1), c=1.363 2(1) nm, α=99.08(1), β=87.11(1), γ=101.94(1)°, V=0.872 1(3) nm 3, Z=2, Dc=1.604 cm -3 , μ=7.73 cm -1 , F (000)= 434. The structure was solved by direct methods and the final R and R w were converged to 0.037 and 0.050, respectively. In the title complex, the manganese atom is six coordinated by two N atoms from phen, two O atoms from the coordinate water molecules and two O atoms from the maleate dianions. Two carboxylate O atoms of each maleate dianion coordinate to two manganese atoms forming an infinite chain. There are two types of H bond in the crystal, the H bonding interaction between the carboxylate O atom and the H atom of the coordinate H 2O and the more complicated interaction among the crystal H 2O molecules, coordinate H 2O molecules and the carboxylate O atoms. The IR peaks at 1 425 and 1 540 cm -1 were assigned to the symmetric and asymmetrical vibrations of the carboxylate group. Broad peaks observed at 3 500～3 100 cm -1 were indicative of H 2O molecules. Thermochemical study shows the loss of lattice H 2O at 60°C and then the coordinate H 2O. Organic ligands begin to decompose at about 300°C and end at 450°C to form MnO.

关 键 词：晶体结构 光谱表征 多核锰配合物 合成 邻菲罗啉 

分 类 号：O614.711[理学—无机化学]