2-(2-苯并咪唑基)-6-甲基吡啶铜(I)铁(II)异双核配合物的合成与表征

摘要

以1,1'-双(二苯基膦)二茂铁(dppf)、2-(2-苯并咪唑基)-6-甲基吡啶(Hbmp)和[Cu(CH3CN)4](ClO4)作为起始原料,合成得到一个铜(I)铁(II)杂金属双核配合物[Cu(Hbmp)(dppf)](ClO4)(1).X-射线单晶衍射结果表明:配合物1是一个铜(I)铁(II)异双核配合物,其中铜(I)离子以四配位方式,分别与2个氮原子和2个磷原子相连接形成一个变形的四面体构型,而铁(II)离子镶嵌在2个环戊二烯基之间构成一个交错式夹心饼干构型.配合物1在355~460 nm有一个弱的低能量宽吸收峰,来源于铜(I)离子到Hbmp配体的金属到配体电荷转移跃迁(MLCT),含有一些dppf到Hbmp的配体到配体电荷转移跃迁(LLCT).%A Cu(I)Fe(II) heterometallic dinuclear complex [Cu(Hbmp)(dppf)](ClO4) (1) was synthesized by using 1,1'-bis(diphenylphosphino)ferrocene (dppf), 2-(2-benzimidazolyl)-6-methyl pyridine (Hbmp) and [Cu(CH3CN)4] (ClO4) as raw materials. As revealed by single-crystal X-ray diffraction, compound 1 is a Cu(I)Fe(II) heterodinuclear complex, in which the Cu(I) ion adopts a four-coordinate mode and connects with two N and two P atoms to form a distorted tetrahedral configuration, while the Fe(II) ion is sandwiched between two cyclopentadienyl moieties to generate a staggered sandwich biscuit geometry. Complex 1 has a weak low-energy broad absorption in the 355~460 nm region, which is assigned to metal-to-ligand charge-transfer (Cu(I)→Hbmp, MLCT) transition, mixed with some ligand-to-ligand charge-transfer (dppf→Hbmp, LLCT) transition.