Synthesis,crystal structures and spectral properties of cobalt (Ⅱ) complexes:[ CoL (N_3) ] ·ClO_4 and CoL (N_3)_2 [L=tris ((3,5-dimethylpyrazol-1-yl) methyl) amine

Two monomeric cobalt(Ⅱ)complexes,[CoL(N3)] ClO4(1)and CoL(N3)2(2),where L is tris((3,5-dimethylpyrazol-1-yl)methyl)amine,were synthesized and their crystal structures were determined by X-ray diffraction technique.Complex 1 is five coordinated with one azide nitrogen atom and four nitrogen atoms of the tris((3,5-dimethylpyrazol-l-yl)-methyl)amine ligand,and the metal center is in distorted trigonal bipyramidal environment.Complex 2 is six coordinated distorted octahedron with the two azide nitrogen atoms and four nitrogen donors of the tris((3,5-dimethylpyrazol-1-yl)-methyl)amine ligand.The solution behaviors of the title complexes have been further investigated by UV-Vis,and 1H NMR analysis.It is found that the formation of 1 and 2 depends on the molar ratio of the azide ion to metal salt and ligand Complex 1 attached with one azide group is more stable and easy to generate than complex 2 incorporated with two azide groups,and the reasons were well discussed.     

二(1-环戊烯基环戊二烯基)四羰基二钌(Ⅰ)的合成与晶体结构

由6,6-四亚甲基富烯与Ru3(CO)12在二甲苯中加热回流,合成了一个新的双核配合物(η5-C10H11)2Ru2(CO)2(μ-CO)2。通过元素分析、红外光谱、核磁共振氢谱对其结构进行了表征,用X射线单晶衍射法测定了配合物的结构,结果表明:晶体属于三斜晶系,P空间群,a=0.641 57(19)nm,b=0.761 3(2)nm,c=1.192 4(3)nm,α=89.973(4)°,β=87.143(4)°,γ=69.666(4)°,V=0.545 3(3)nm3,Dc=1.756 g·cm-3,μ=1.412 mm-1,F(000)=286,Z=1,R1=0.024 0,wR2=0.066 7。晶体结构表明6,6-四亚甲基富烯在反应过程中发生了双键的异构。     

芳基取代四甲基环戊二烯基铼羰基化合物的合成、晶体结构及催化性能

芳基取代的四甲基环戊二烯 C₅HMe₄Ar（Ar=Ph,4-CH₃Ph,4-OCH₃Ph,4-ClPh,4-BrPh） 分别与Re₂（CO）₁₀在二甲苯中加热回流,得到了5个单核配合物[（η⁵-C₅Me₄Ar）Re（CO）₃]（Ar=Ph （1）,4-CH₃Ph （2）,4-OCH₃Ph （3）,4-ClPh （4）,4-BrPh （5）]。通过元素分析、红外光谱、核磁共振氢谱对配合物1~5的结构进行了表征,用X射线单晶衍射法测定了配合物的结构。同时,研究了这五种配合物在芳香族化合物Friedel-Crafts烷基化反应中的催化活性。     

取代四甲基环戊二烯基钌羰基化合物的合成及结构

将配体[C5Me4HR](R=cyclopentyl,cyclohexyl,nPr)分别与Ru3(CO)12在二甲苯中加热回流,合成了3个新的双核配合物[(η5-C5Me4R)Ru(CO)(μ-CO)]2(R=cyclopentyl(1),cyclohexyl(2),nPr(3))。利用红外光谱、元素分析、核磁共振氢谱对它们的结构进行了表征,用X-射线单晶衍射法测定了1和2的结构。