二茂金属共轭大环配体配合物的结构及性质

报道了配体Ｎ－（二茂铁基甲基）－１，４，７－氮杂－９－冠－３（Ｌ１）和Ｎ－（二茂钌基甲基）－１，４，７－氮杂－９－冠－３（Ｌ２）的Ｃｏ（Ⅲ）和Ｆｅ（Ⅲ）配合物１－４的合成及电化学性质，配合物「Ｃｏ（Ⅲ）（Ｌ１）２（ＡｃＯ）２（ＯＨ）」（ＣｌＯ４）（Ｉ）２（１）的晶体结构显示这些配合物具有线型排列的四金属中心结构，电化学研究表明：在这些配合物中，客体金属离子通过分子片断的电子传递作用使二茂金属的金属

Syntheses, Crystal Structure and Properties of Complexes of Metallocene- conjugated Macrocyclic Ligand

Four complexes ([Co(III)2(L1)2(AcO)2(OH)](AcO)(I)2 4H2O 1, [Fe(III)2(L1)2 (AcO)2(OH)](ClO4)2(I)2, [Co(III)2(L1)2(AcO)2(OH)](ClO4)34H2O3, and[Fe(III)2(L1)2 (AcO)2(OH)](AcO)(C1O4)2 4H2O 4) (where L1 = N - ferrocenylmethyl - 1,4,7 - triazacyclononane and L2 = N - ruthenocenylmethyl - 1,4,7 - triazacyclononane). were synthesised and characterized. Crystal structure of 1 shows that the complexes have a linearly arranged four - core skeleton which can be depicted as Mc -B-M-B'-M-B- Me (where Mc represents metallocenylCunit, B and B' represent bridging groups) . Electrochemical investigation of these complexes confirms that introduction of the guest metal ions, M, onto the free ligand induces an anodic shift of the redox potential of metallocene and, at the same time, that coordination of ligand to the metal ions causes change in the electrochemical behavior of the guest ion. No interaction is observed between two metallocene components separated by TACN - M ( III) fragment, but an interaction between two guest ions is emphasized by the capture of mix - valence species during the course of electrochemical investigation.