含2，4－二硫代乙内酰脲分子片卡宾铁羰基簇合物的合成和结构  

Syntheses and Structures of Trinuclear Iron Carbonyl ClustersContaining Carbenes from Cleaving of 2,4-Dithiohydantoins

作　　者：刘登奎[1] 成庆民[1] 胡襄[1] 刘启旺[1] 刘树堂[1] 

机构地区：[1]内蒙古大学化学系

出　　处：《高等学校化学学报》1995年第5期678-682,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金;中国科学院福州物构所结构化学开放实验室资助

摘　　要：Ｆｅ３（ＣＯ）１２与５个２，４－二硫代乙内酰脲ＳＣＮＨＣ（Ｒ１）（Ｒ２）Ｃ（Ｓ）ＮＨ应制得通式为Ｆｅ３（ＣＯ）８（μ３－Ｓ）２（Ｌ）含卡宾配体的５个新铁羰基簇合物（１～５）对其进行了元素分析，ＩＲ、ＨＮＭＲ和ＭＳ表征，并用Ｘ射线衍射法测定了簇合物３的晶体和分子结构，表明２，４－二硫代乙内酰脲分子片配位基：ＣＮＨＣ（ＣＨ３）２Ｃ（Ｓ）ＮＨ的卡宾碳具有ｓｐ＾２成键特征，其Ｃ－Ｆｅ键长０．１８９８ｎｍ，The reaction of Fe3 (CO )12 with 2 , 4-dithiohydantoins SCNHC(R1) (R2)C(S)NH (SL) yields the known Fe3 (CO)9(u3-S)2 and the five new open triangular iron carbonyl clus ters Fe3(CO)8(u3-S)2(L) 1-5. It was found that the coordinated ligands in the clusters 1-5 besides eight terminal CO ligands are two sulfito S atoms and a heterocyclic carbene L which was formed from the cleavage of the ligand precursor SL. The formulas and structures of these clusters were characterized by elementary analysis, IR, 1H NMR and MS techniques and the molecular structure of 3 was determined by X-ray diffraction analysis. The sp2 bond ing character of the carbon (carbene) atom of fragmental 2,4-dithiohydantoin : CNHC(CH3)2C(S)NH shown clearly in 3 and the Ccarh.-Fe bond length of 0. 1898 nm cor responds to other iron stabilized carbenes. This carbene ligand displaced a terminal axial CO of the basal Fe (1) atom and locates in a vertical position to the Fe (1)S(1)Fe (3)S(2) distort ed basal plane. The geometry of Fe, (CO)9 (u3-S)2 has been maintained in 3, but some of Fe-S and Fe-Fe bond lengths have been changed.

关 键 词：铁 羰基 簇合物 卡宾 二硫代乙内酰脲 合成 结构 

分 类 号：O614.811[理学—无机化学] O766.3[理学—化学]