锌二硫代氨基甲酸配合物的合成、晶体结构及其热稳定性研究  

Synthesis, Struture and Thermal Stability of Zinc Complexes with Dithiocarbamate

作　　者：钟昀[1] 章伟光[2] 张启交[2] 谭民裕[1] 王素蘭 

机构地区：[1]兰州大学化学化工学院,兰州730000 [2]华南师范大学化学系,广州510631 [3]国立清华大学化学系

出　　处：《化学学报》2003年第11期1828-1833,共6页Acta Chimica Sinica

基　　金：广东省自然科学基金 (No.990 4 63)

摘　　要：合成了 3个二硫代氨基甲酸锌配合物 [Zn2 (S2 CNBun2 ) 4 ] ( 1) ,[Zn(S2 CNBy2 ) 2 ] ( 2 )和 [Zn(S2 CNBy2 ) 2 Py] ( 3 ) (Bun=正丁基 ,By =苄基 ,Py =吡啶 ) .测定了它们的晶体结构 ,红外光谱和热稳定性 .1为单斜晶系 ,空间群C2 /c,晶胞参数a =2 3 3 2 9( 3 )nm ,b =1 70 90 ( 2 )nm ,c =1 6115 ( 2 )nm .α =90° ,β =12 7 5 60 ( 10 )° ,γ =90° .2为正交晶系 ,空间群Pbcn ,晶胞参数a =1 62 193 ( 11)nm ,b =1 90 0 10 ( 12 )nm ,c =0 93 795 ( 6)nm .α =90° ,β =90° ,γ =90° .3为三斜晶系 ,空间群P 1,晶胞参数a =0 864 18( 6)nm ,b =1 3 115 6( 9)nm ,c =1 662 3 8( 11)nm .α =10 6 3 98( 1)° ,β =92 63 3 ( 1)° ,γ =10 7 461( 1)° .1为二聚体 ,属典型的荒氨酸金属配合物结构类型 .2为一单核四配位化合物 ,而在荒氨酸金属配合物中 (除Ln ,Ac系外 )该结构类型非常少见 .2中引入吡啶环得到 3 ,3为一五配位化合物 ,吡啶环的引入说明 2的中心离子处于配位不饱和状态 ,这与以往报道相吻合 .1的热稳定性质研究发现其在 2 5 1℃有升华现象 。Three zinc complexes with dithiocarbamate were synthesized. They are [Zn-2 (S(2)CNBu(2)n)(4)] (1), [Zn(S(2)CNBy(2))(2)] (2) and [Zn(S(2)CNBy(2))(2)Py] (3) (where By = benzyl, Py = pyridine). Their crystal structure, IR spectra and thermal stability were determined. 1 is monoclinic, space group C2/c, with a = 2.3329(3) nm, b = 1.7090(2) nm, c = 1.6115(2) nm. alpha = 90degrees, beta = 127.560(10)degrees, gamma = 90degrees. 2 is orthorhombic, space group Pbcn, with a = 1.6219(11) nm, b = 1.9001(12) nm, c = 0.9376(6) nm. alpha = 90degrees, beta = 90degrees, gamma = 90degrees. 3 is triclinic, space group P-1, with a = 0.8642 (6) nm, b = 1.3116 (9) nm, c = 1.6624 (11) nm. alpha = 106.398 (1)degrees, beta = 92.633(1)degrees, gamma = 107.461 (1)degrees. Compound 1 is dimeric, which belongs to the typical structure of metal dithiocarbamate complexes. 2 is monomeric which is seldom appeared in metal (except Ln, Ac series) complexes with dithiocarbamate. 2 could coordinate with pyridine to form 3. 3 is a five-coordinated complex. It is indicated that the center metal ion of 2 is unsaturated, which is the same as some in the existed reports. The thermal stability of 1 shows that it could sublime at 251 degreesC, so 1 may be precursor for MOCVD.

关 键 词：锌二硫代氨基甲酸配合物 合成 晶体结构 热稳定性 [Zn2(S2CNBu2^n)4] [Zn(S2CNBy2)2] [Zn(S2CNBy2)2Py] 

分 类 号：O641.4[理学—物理化学]