含杂环卡宾铁羰基簇合物的合成和结构  

Syntheses and Structures of Heterocyclic Carbene——Containing Iron Carbonyl Clusters

作　　者：安金[1] 胡襄[1] 刘树堂[1] 刘启旺[1] 吴秉芳[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》1992年第10期1033-1040,共8页Acta Chimica Sinica

基　　金：国家自然科学基金;内蒙古自然科学基金

摘　　要：Fe_3(CO)_(12)与杂环硫代酰胺S=CNHAX=(SLH,其中A=去氢烃基;X=S,O,NH)反应,在生成Fe_3(CO)_9(μ_3-S)_2的同时,还得到SLH劈开后以杂环卡宾LH配位的新羰合铁簇(1—6):Fe_3(CO)_8(μ_3)_2(LH)(LH分别为:L_1H=:CNH(CH_2)_2O,1:L_2H=:CNH(CH_2)_3O,2;L_3H=:CNHCH(C_2H_5)CH_2O,3;L_4H=:CNHC(CH)_4CO,4;L_5H=:CNHC(CH)_4CNH,5;L_6H=:CNHCH(C_2H_5)CH_2S,6).对它们进行了元素分析、IR、~1H NMR和MS表征,并测定了5的晶体和分子结构.表明杂环分子片:CNHC(CH)_4CNH的卡宾碳具有sp^2成键特征,其C_(卡賓)—Fe键长0.1916nm,与其它铁卡宾配合物的键长一致.卡宾取代了Fe(1)S(1)Fe(2)S(2)基底平面的Fe(1)原子上轴向位置的羰基CO.5的分子几何形状基本维持Fe_3(CO)_9(μ_3-S)_2的形状,但某些Fe—S键长有所改变.The reaction of Fe_3(CO)_(12) with heterocyclic thioamides S=CNHAX (SLH, where x=S,O, NH) yields the Fe_3(CO)_9(μ_3~S)_2 and the new open triangelar iron carbonyl clusters Fe_3(CO)_8(μ_3-S)_2(LH)1—6. It was found that the coordinated ligands in the product clusters are the sulfito S and heterocyclic carbene LH which was formed from the cleavage of the precursor SLH. where L_1H= :CNH(CH_2)_2O, 1; L_2H=:CNH(CH_2)_3, 2; L_3H=:CNHCH(C_2H_5)CH_2O, 3; L_4H=:CNHC(CH)_4CO, 4; L_5H=:CNHC(CH)_4CNH, 5; L_6H=:CNHCH(C_2H_5)CH_2S, 6; The formulas and structures of these clusters were characterized by elemental analysis, IE, ~1H NMR, MS techniques and the molecular structures of 5 was obtained by X-ray diffraction analysis. The sp^2 bonding character of the carbon (carbene) atom of fragmental heterocyclic thio amide: CNHC(CH)_4CNH was clearly shown in 5 and the Cearbene-Fe bond length of 0.1916nm corresponds to other ironstabilized carbenes. This carbene ligand displaces a terminal axial CO of the basal Fe(l) atom and locates in a vertical position to the Fe(l)S(l)Fe(2)S(2) distorted basal plane. The geometry of Fe_3(CO)_9(μ_3-S)_2 has been maintained in 5. but some of the Fe-S bond lengths have been changed.

关 键 词：铁羰基簇合物 金属卡宾 络合物 

分 类 号：O614.811[理学—无机化学]