硅基取代及硅桥连双环戊二烯基四羰基二铁与HgCl_2的反应及产物结构研究  

Reaction of Silyl-Substituted and Sila-Bridged Biscyclopentadienyl Tetracarbonyl Diiron with HgCl_2 and Structures of the Products

作　　者：谢文华[1] 周秀中[1] 徐善生[1] 王宏根[2] 王如骥[2] 

机构地区：[1]南开大学化学系,天津300071 [2]南开大学中心实验室,天津300071

出　　处：《化学学报》1995年第11期1131-1136,共6页Acta Chimica Sinica

基　　金：国家自然科学基金;国家教委博士学科点基金资助课题.

摘　　要：二(硅基取代环戊二烯基)四羰基二铁化合物[η~5-RC_5H_4Fe(CO)]_2(μ-CO)_2(R=SiMe_3,1;Si_2Me_5,2)与HgCl_2反应得到预期的Fe—Fe键被断裂的铁氯化物6(R=SiMe_3)和8(R=Si_2Me_5)及铁氯汞化物5(R=SiMe_3)和7(R=Si_2Me_5).硅桥连的类似物R^1[η~5-C_5H_4Fe(CO)]_2(μ-CO)_2(R^1=SiMe_2,3;SiMe_2OSiMe_2,4)由上述反应除得到预期产物外,还分离到相应的歧化产物R^1[η~5-C_5H_4Fe(CO)_2HgCl]_2(R^1=SiMe_2,10;SiMe_2OSiMe_2,13)与R^1[η~5-C_5H_4Fe(CO)_2Cl]_2(R^1=SiMe_2,11;SiMe_2OSiMe_2,14),讨论了歧化产物的生成原因.对产物5～14的结构用元素分析、IR,~1H NMR进行了表征,并测定了5的晶体结构.5为单斜晶系,空间群P2_1/n,α=1.1648(3),b=0.7484(4),c=1.6823(5)nm,β=106.55(2)°,V=1.405(2)nm^3,Z=4,D_x=2.29g·cm^(-3).Reactions of bis(silylcyclopentadienyl) tetracarbonyl diiron compounds [n5-RC5H4Fe-(CO)]2(μ-CO)2(R=SiMe3, 1; Si2Me5, 2) with HgCl2 resulted in cleavage of Fe-Fe bond and gave expected products 5-8, while from the corresponding reactions of bridged analogues R1[n5-C5H4Fe(CO)]2(μ-CO)2(R1=SiMe2, 3; SiMe2OSiMe2,4), unexpected products of disproportionation were isolated, as well as the expected ones. The occurrence of the disproportionation was investigated. All the products were characterized by IR, 1H NMR and elemental analysis. The crystal structure of 5 was determined. The crystals of 5 are monoclinic, space group P21 / n with a = 1.1648(3), 6 = 0.7484(4), c = 1.6823(5) nm and β= 106.55(2)°, V = 1.405(2)nm3, Z=4, Dx = 2.29g·cm-3.

关 键 词：环戊二烯 二氯化汞 歧化 四羰基二铁 

分 类 号：O627.81[理学—有机化学] O614.243[理学—化学]