四甲基二硅桥连二(1-苯基环己基环戊二烯基)四羰基二铁的合成、结构及热重排反应研究

The Synthesis, Structure and Thermal Rearrangement Reaction of Tetramethyldisilane-bridged Bis(1-phenylcyclohexylcyclopentadienyl)tetracarbonyl Diiron

1,2 -二 ( 1 -苯基环己基环戊二烯基 )四甲基二硅烷与 Fe( CO) 5在二甲苯中加热回流生成二铁化合物( Me2 Si Si Me2 ) [( 1 -Ph-c-C6H10 C5H3 ) Fe( CO) ]2 ( μ-CO) 2 ( 2 ) .通过柱层析分离到化合物 2的顺反异构体 2 c和2 t,并分别进行热重排反应 ,发现顺式底物 2 c重排生成反式重排产物 [Me2 Si( c-C6H10 Ph C5H3 ) Fe( CO) 2 ]2( 3 t) ,而反式底物 2 t重排则生成顺式重排产物 3 c.这表明重排反应是立体专一性的 .通过 X射线衍射分析测定了化合物 2 c和 3 t的晶体结构 .

The reaction of 1,2-bis(1-phenylcyclohexylcyclopentadineyl)tetramethyldisilane with Fe(CO) 5 in refluxing xylene afforded the diiron complex(Me 2SiSiMe 2)[(1-Ph-c-C 6H 10C 5H 3)Fe· (CO)] 2( μ-CO) 2(2), existing as a mixture of cis and trans isomers(2c and 2t), which were separated by column chromatography. When the two isomers were heated in refluxing xylene, the cis substrate(2c) rearranged to the trans product[Me 2Si(1-Ph-c-C 6H 10C 5H 3)Fe(CO) 2] 2(3t), while the trans substrate(2t) yielded the cis product(3c), respectively. This indicates that the rearrangement reaction is stereospecific. The molecular structures of compound 3c and 4t were determined by X-ray diffraction analysis.