N,N-二苄基二硫代氨基甲酸金属配合物的合成、晶体结构及其热稳定性研究  

Synthesis, Structure and Thermal Stability of Metal Complexes with N,N-Dibenzyl Dithiocarbamate

作　　者：范军[1] 殷霞[1] 章伟光[1] 张启交[1] Lai Chian-Sing Tiekink Edward R.T. 范毅[3] 黄庙由[3] 

机构地区：[1]华南师范大学化学系,广州510631 [2]新加坡国立大学化学系,新加坡117543 [3]华南理工大学高分子材料科学与工程系,广州510641

出　　处：《化学学报》2004年第17期1626-1634,共9页Acta Chimica Sinica

基　　金：广东省自然科学基金 (No.990 4 63);广东省教育厅自然科学基金 (No.1 999 89);新加坡国立大学 (No.R 1 4 3 0 0 0 2 1 3 1 1 2 )资助项目

摘　　要：报道了四种二苄基二硫代氨基甲酸金属配合物 [Cd(DBTC) 2 ] 2 ( 1) ,[Hg(DBTC) 2 ] ( 2 ) ,[Nd(DBTC) 3 ·2H2 O]和 [Nd (DBTC) 3 (HMPA) 2 ] ( 3 ) (DBTC =N ,N 二苄基二硫代氨基甲酸 ;HMPA =六次甲基磷酰胺 )的合成及其红外光谱 .配合物 1～3的晶体结构用X射线晶体衍射分析确定 .配合物 1,C3 0 H2 8N2 CdS4,Mr=65 7.18,单斜晶系 ,空间群P2 1/n ,a =1.110 98( 4 )nm ,b =1.5 63 2 5 ( 5 )nm ,c =1.66695 ( 5 )nm ,β =97.92 2 0 ( 10 )° ,Z =4,R =0 .0 44 ,wR1=0 .0 91.2 ,C3 0 H2 8N2 HgS4,Mr=745 3 7,正交晶系 ,空间群Pbcn ,a =1.64 73 8( 1)nm ,b =1.864 18( 14 )nm ,c =0 .940 0 0 ( 6)nm ,Z =4,R =0 .0 3 87,wR1=0 0 965 .3 ,C57H78N9NdO2 P2 S6,Mr=13 19.82 ,单斜晶系 ,空间群P2 1/c ,a =1.3 0 3 89( 9)nm ,b =3 .470 8( 3 )nm ,c=3 .12 10 ( 2 )nm ,β =96.5 2 7( 2 )° ,Z =8,R =0 .10 2 3 ,wR1=0 .2 2 0 3 .1为二聚体 ,中心离子的配位结构为扭曲的四方锥 ;2和 3均为单核配合物 ,但中心离子的配位结构不同 ,2为扭曲的四面体 ,而 3则为变形的十二面体 .配合物的热重分析结果表明配合物 1,2在加热失重的过程中可能伴随有升华现象 。Four metal complexes, which were shown as [Cd(DBTC)(2)](2) (1), [Hg(DBTC)(2)] (2), [Nd(DBTC)(3).2H(2)O] and [Nd(DBTC)(3)(HMPA)(2)] (3) (where DBTC = N,N-dibenzyl dithiocarbamate, HMPA = hexamethylphosphoramide), were synthesized and characterized by IR spectra. The structures of complexes 1 similar to 3 were determined by X-ray crystallography analysis. Crystal data of compound 1: C(30)H(28)N(2)CdS(4), M(r) = 657.18, monoclinic, space group P2(1)/n, a = 1.11098(4) nm, b = 1.56325(5) nm, c = 1.66695(5) nm, beta = 97.9220(10)degrees, Z = 4, R = 0.044, wR(1) = 0.091. Crystal data of compound 2: C(30)H(28)N(2)HgS(4), M(r) = 745.37, orthorhombic, space group Pbcn, a = 1.64738 (1) run, b = 1.86418 (14) nm, c = 0.94000 (6) nm, Z = 4, R = 0.0387, wR(1) = 0.0965. Crystal data of compound 3: C(57)H(78)N(9)NdO(2)P(2)S(6), M(r) = 1319.82, monoclinic, space group P2(1)/c, a = 1.30389 (9) nm, b = 3.4708(3) nm, c = 3.1210 (2) nm, beta = 96.527(2)degrees, Z = 8, R = 0.1023, wR(1) = 0.2203. Compound 1 is a dimer, and the Cd(II) ion has an approximate tetragonal pyramidal geometry. Compounds 2 and 3 are monomers and show different coordination polyhedron. The Hg(II) ion has a distorted tetrahedral coordination polyhedron, while the Nd(III) ion exhibits distorted dodecahedral geometry. Thermal gravity (TG) data indicate that compounds 1 and 2 may be sublimed and decomposed in the course of heating and they might be expected to be useful precursors for MOCVD.

关 键 词：N N-二苄基二硫代氨基甲酸 镉配合物 汞配合物 合成 晶体结构 热稳定性 

分 类 号：O641.4[理学—物理化学] O623.627[理学—化学]