硅基取代及硅桥连双环戊二烯基四羰基二铁与HgCl2的反应及产物结构研究

二(硅基取代环戊二烯基)四羰基二铁化合物η^5-RC5H4Fe(CO)]2(μ-CO)2(R=SiMe3, 1; Si2Me5, 2)与HgCl2反应得到的预期的Fe-Fe键被断裂的铁氯化物6(R=SiMe3)和8(R=Si2Me5)及铁氯汞化物5(R=SiMe3)和7(R=Si2Me5)。硅桥连的类似物R^1η^5-C5H4Fe(CO)]2(μ-CO)2(R^1=SiMe2, 3; SiMe2OSiMe2, 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^1η^5-C5H4Fe(CO)2HgCl](R^1=SiMe2, 10; SiMe2OSiMe2, 13)与R^1η^5-C5H4Fe(CO)2Cl]2(R^1=SiMe2, 11; SiMe2OSiMe2, 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P21/n, a=1.1648(3), b=0.7484(4),c=1.6823(5)nm, β=106.55(2)°, V=1.405(2)nm^3, Z=4, Dx=2.29g.cm^-^3。

Reaction of silyl-substituted and sila-bridged biscyclopentadienyl tetracarbonyl diiron with HgCl2 and structures of the products

Reactions of bis(silylcyclopentadienyl) tetracarbonyl diiron compounds η^5-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 R^1η ^5-RC5H4Fe(CO)]2(μ-CO)2(R^1=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 P2/1m with a=1.1648(3), b=0.7484(4), c=1.6823(5)nm and β=106.55(2)°, V=1.405(2)nm^3, Z=4, Dx=2.29g.cm^-^3.