四钼簇合物Mo_4(μ_3—O)_2O_4Cl_2(OCOC_6H_5)_6和[Mo_4(μ_3—O)_2O_4Cl_2(OCOC_6H_4CH_3)_6]·2C_6H_5Cl的合成、结构、反应机理及光谱性质研究  

SYNTHESES, STRUCTURES, REACTION MECHANISMS AND SPECTRA OF CLUSTERS Mo(_4(μ3-O)2 O_4C1_2(OCOC_6H_5)_6 AND (Mo4(μ3-O)_2O_4 C1_2(OCOC_6H_4CH_3)_6)·2C_6H_5C1

作　　者：姜燕[1] 樊玉国[2] 孙春亭[2] 李铁津 

机构地区：[1]大连理工大学化工学院应用化学系物理化学教研室,吉林大学化学系长春130023 [2]吉林大学化学系,长春130023

出　　处：《无机化学学报》1990年第3期261-266,共6页Chinese Journal of Inorganic Chemistry

摘　　要：用MoCl_5和C_ 6H_5COOH(或CH_3C6H_4COOH)在氯苯溶液中反应,得到四钼簇合物Mo_4(μ_3-O)_2O_4Cl_2-(OCOC_6H_5)_6(或[Mo_4(μ_3-O)_2O_4Cl_2(OCOC_6H_4CH_3)_6]·2C_6H_5Cl)晶体。用X射线单晶衍射法测定了簇合物的晶体结构,运用18电子规则及簇合物的晶体结构数据,得到金属Mo-Mo键键价为1,钼在簇合物中均呈+5价。进行了反应机理的探讨,簇合物中端基氧和桥基氧的存在来自于苯甲酸(对甲基苯甲酸),MoCl_5和C_6H_5COOH(CH_3C_6H_4COOH)作用时,首先生成钼的含氧配合物MoOCl_3,然后生成双核钼配合物Mo_2(μ_2-O)_2O_2Cl_2,进一步形成配合物。红外光谱、激光拉曼光谱和磁化率的测定证明了结构分析的结果。值得注意的是,固体表面光电压谱和固体光声光谱的测定,簇合物Mo_4(μ_3-O)_2O_4Cl_2(OCOC_6H_5)_6的表面光电压谱在～600nm处有一光致电荷分离谱带。Tetranuclear complexes MO4(μ3-O)2O4Cl2(OCOC6H5)6 and (Mo4(μ3-O)2O4Cl2(OCOC6H4 CH3)6·2C6H5Cl were produced. The Crystal structures were defined by a four-circle X-ray diffractometer. The IR and R spectra were recorded in the 200-4000cm-1 and 50-1050cm-1 range.The spectra of surface photovoltaic and photoacoustic were also recorded in the wave-length range of 450-800 nm. The single Mo-Mo bond and Mo (V) ion in clusters were determined. The reaction mechanisms of clusters were, discussed. It is worth considering carefully that SPV has one broad photocharge separation band at about 600 nm.

关 键 词：钼簇合物 合成 结构 光谱 

分 类 号：O614.612[理学—无机化学]