含硫氮杂环卡宾铁羰基簇合物的合成和结构  

Synthesis and Structures of Trinuclear Iron Carbonyl Clusters with S,N-Containing Heterocyclic Carbene Ligands

作　　者：刘兵[1] 吴秉芳[1] 胡襄[1] 刘树堂[1] 刘启旺[1] 赵志蓉[1] 

机构地区：[1]内蒙古大学化学系,呼和浩特010021

出　　处：《化学学报》1998年第9期930-936,共7页Acta Chimica Sinica

基　　金：国家自然科学基金(29661001);南京大学配位化学所国家开放实验室资助课题

摘　　要：Fe_3(CO)_(12)与4个S,N取代的杂环硫代酰胺配前体[SCSC(SR)NNPh(SL_n),其中SL_1:R=Me;SL_2:R=Et;SL_3:R=n-Pr;SL_4:R=i-Bu]反应,合成得到含硫氮杂环卡宾配体的通式为[Fe_3(CO)_8(μ_3-S)_2L]的4个新羧合铁簇合物(1～4).其配体S原子和杂环卡宾L皆来自配前体SL的劈开.对它们进行了元素分析,IR,~2H NMR和MS表征,并用X射线衍射测定了2的晶体分子结构,表明含硫氮杂环分子片CSC(SR)NNPh(L)的卡宾碳具有sp^2成键特征,其C_(卡宾)键长为0.1960nm.2的分子几何构型维持母体物[Fe_3(CO)_9(μ_3-S)_2]的形状,其中卡宾基取代四方锥分子骨架Fe_3S_2基底平面Fe(1)S(1)Fe(3)S(2)的Fe(3)原子上径向位置的一个端羰基CO.The reaction of [ Fe3 (CO) 12 ] with four S, N - substituted heterocyclic thioamides[SCSC(SR)NNPh(SLn, where SL1: R=Me; SL2: R = Et; SL3: R=n-pr; SL4: R=i-Bu) ] yields new open triangelar iron carbonyl clusters [Fe3(CO)3(μ3 - S)2L]1~4. It was found that the coordinated ligands in the product clusters were two sulfito S atoms and a heterocyclic carbene L which was formed from the cleavage of the ligand precursor SLn . The formulas and structures of these clusters were characterized by elemental analysis, IR, 1H NMR, and MS techniques and the molecular structures of 2 was determined by X - ray diffraction analysis. The sp2 bonding character of the carbon (carbene) atom of fragmental S, N - substituted heterocyclicthioamides CSC(SEt)NNPh(L2) is showed clearly in 2 and the Ccarbene- Fe bond length of 0. 1960nm corresponds to other iron stabilized carbenes. This carbene ligand displaces a terminal radial CD of the basal Fe(3) atom and locates in an essentially coplanar position to the Fe(1)S(1) Fe(3)S(2) distorted basal plane. The open triangular geometry of the matrix cluster [Fe3(CO)9(μ3 - S)2]with a distorted Fe3S2 square pyramidal framework has been maintained in 2.

关 键 词：铁羰基簇合物 金属卡宾 硫氮杂环 铁羰基硫簇 

分 类 号：O627.81[理学—有机化学]