二价钐配合物和异氰酸苯酯的反应——[(CH_3C_5H_4)_2(THF)Sm]_2[μ-η~4-(PhN)OCCO(NPh)]·2THF的合成、晶体结构及其催化性能

Reaction of Divalent Samarium Complexes with Phenyl Isocyanate Synthesis, Molecular Structure and Catalytic Activity of [(CH_3C_5H_4)_2(THF)Sm]_2[μ-η~4-(PhN)OCCO(NPh)]·2THF

报道了二价配合物 ( CH3C5H4) 2 Sm( THF)和 Sm I2 ( THF) x 与异氰酸苯酯的反应 . ( CH3C5H4) 2 Sm( THF)和异氰酸苯酯反应生成配合物 [( CH3C5H4) 2 ( THF) Sm]2 [μ-η4-( Ph N) OCCO( NPh) ]· 2 THF( 1 ) ,而Sm I2 ( THF) x则被异氰酸苯酯氧化为 [Sm I2 ( THF) 5][Sm I4( THF) 2 ]. ( CH3C5H4) 2 Sm( THF)和配合物 1都能催化异氰酸苯酯的齐聚反应 .( CH3C5H4) 2 Sm( THF)和异氰酸苯酯作用生成配合物 1的反应可以认为是( CH3C5H4) 2 Sm( THF)催化异氰酸苯酯齐聚的引发反应 ,而配合物 1是该齐聚反应的活性中间体 . X射线衍射分析表明 ,配合物

This article describes the reaction of divalent complexes (CH 3C 5H 4) 2Sm(THF) and SmI 2(THF) x with phenyl isocyanate.(CH 3C 5H 4) 2Sm(THF) reacts with phenyl isocyanate to give the product of [(CH 3C 5H 4) 2(THF)Sm] 2[ μ η 4 (PhN)OCCO(NPh)]·2THF(1), while SmI 2(THF) x was oxidated to be [SmI 2(THF) 5][SmI 4(THF) 2] in PhNCO solution. (CH 3C 5H 4) 2Sm(THF) and complex 1 display a catalytic activity for the oligomerization of phenyl isocyanate. The reaction of(CH 3C 5H 4) 2Sm(THF) with PhNCO to form complex 1 can be thought as the initiation reaction and complex 1 may be considered to be the real active species for the PhNCO oligomerization with the catalyst of(CH 3C 5H 4) 2Sm(THF). The structure of complex 1 was determined by X ray diffraction analysis and confirmed to be a bimetallic complex with a dianionic oxamide ligand.