Co3（CO）7（μ3—S）（μ,η^2—SCNR2）的合成和晶体结构  

Syntheses and Crystalline Structures of Clusters Co_3(CO)_ 7(μ_3-S)(μ,η~2-SCNR_2)

作　　者：李松波[1] 刘树堂[1] 胡襄[1] 吴秉芳[1] 常菲[1] 邢彦[2] 贾恒庆[2] 白石英[2] 林永华[2] 

机构地区：[1]内蒙古大学化学系,呼和浩特010021 [2]中国科学院长春应用化学研究所,长春130022

出　　处：《高等学校化学学报》1999年第12期1827-1831,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金!(批准号 :29661001)资助课题

摘　　要：Co2 (CO) 8 与 4个二硫代双 (烷基硫代甲酰胺 )类前配体 [R2 NC(S) S]2 反应 ,得 4个含烷基硫代甲酰胺基的三核钴羰基硫簇合物 .通过元素分析、IR、 1H NMR和 MS等方法表征了它们的结构 ,用 X射线衍射法测定了其中一个簇合物 Co3 (CO) 7(μ3 - S) [μ,η2 - SCN(i- Pr) 2 ]( )的晶体结构 .晶体属单斜晶系 ,P2 1/n空间群 ,晶胞参数 a=1.1452 (2 ) nm,b=1.50 2 8(3) nm,c=1.2 144 (2 ) nm,α=90°,β =92 .15(3)°,γ =90°,V =2 .0 885(7) nm3 ,Z=4 ,F (0 0 0 ) =10 96 ,Dc=1.74 7mg· m-3 ,GOF(F2 ) =0 .835,μ=2 .588nm-1.最终因子 R[I>2 σ(I) ]=0 . 0 4 0 7,Rw=0 .0 6 2Through the reaction of Co 2(CO) 8 with four thiuram [R 2NC(S)S] 2, four new sulfur capped trinuclear cobalt carbonyl clusters Co 3(CO) 7( μ 3 S)( μ, η 2 S *C *NR 2)(Ⅰ: R=Me; Ⅱ: R=Et; Ⅲ: R= i Pr; Ⅳ: NR= N ], were prepared and characterized by elementary analysis, IR, 1H NMR and MS spectroscopy. The crystal structure of the cluster Co 3(CO) 7( μ 3 S)[ μ, η 2 S *C *N( i Pr) 2] (Ⅲ) was determined by X ray single crystal diffraction method. The crystal of Ⅲ is monoclinic, belonging to space group P2 1/n , and the cell parameters are as follows: a =1.145 2(2) nm, b =1.502 8(3) nm, c =1.214 4(2) nm; α =90°, β =92.15(3)°, γ =90°; V =2.088 5(7) nm 3, Z =4, F (000)=1 096, D c=1.747 mg·m -3 , μ =2.588 mm -1 , R =0.040 7, R w=0.062 4. The structural analysis shows that cluster Ⅲ has a pyrimidal Co 3S framework and contains a heterocylic bridging bidentate ligand[ μ , η 2 S *C *N( i Pr) 2] linked to the Co2 and Co3 atoms of the cluster by a cobalt carbon and a cobalt sulfur bond respectively.

关 键 词：钴羰基硫簇合物 烷基硫代甲酰胺 合成 

分 类 号：O614.812[理学—无机化学]