作者:Lea T. Dulatas、Seth N. Brown、Edema Ojomo、Bruce C. Noll、Matthew J. Cavo、Paul B. Holt、Matthew M. Wopperer
DOI:10.1021/ic901683c
日期:2009.11.16
trimethylsilyl chloride. Metathesis with catechol leads to the bis(o-hydroxyphenoxide) complex rather than the chelating catecholate complex. Hydrolysis selectively gives the μ-oxo trimer (Δ,Δ,Δ)/(Λ,Λ,Λ)-(Fc2Bob)Ti(μ-O)}3. The solid-state structures of the μ-oxo trimer and the bis(o-hydroxyphenoxide) complex show that the ferrocene substituents are oriented proximal to the biphenyl backbone rather than
通过乙酰二茂铁和2,2'-联苯二乙酰氯的克莱森缩合制备四齿双(二茂铁基二酮酸酯)配体Fc 2 BobH 2,并用异丙氧基钛(IV)进行金属化,得到(Fc 2 Bob)Ti(O i Pr )2,收率良好。异丙醇基团在用相应的酸处理时被磷酸二(4-硝基苯基)酯基团取代,而在三甲基甲硅烷基氯处理时被氯化物取代。与邻苯二酚的复分解反应生成双(邻羟基苯酚)复合物,而不是螯合的邻苯二酚复合物。水解选择性产生μ-氧三聚体(Δ,Δ,Δ)/(Λ,Λ,Λ)-(Fc 2 Bob)Ti(μ-O)} 3。μ-氧代三聚体和双(邻-羟基苯氧基)配合物的固态结构表明,二茂铁取代基的取向接近联苯骨架,而不是指向外源基团。配合物显示出显着的颜色变化,取决于结合的阴离子,范围从红色异丙醇(λmax = 489 nm)到绿色双(二(4-硝基苯基)磷酸酯)(λmax= 653 nm)。二茂铁的氧化电势在钛环境下显示出适度的变化,