茂铁基稀土铈配合物的合成与结构

本文利用单羧基二茂铁Fc-COOH和1，1′-二羧基二茂铁HOOC-Fc-COOH作为配体分别合成了双核铈配合物Ce₂(FcCOO)₆ (1)和二维层状配位聚合物Ce₂(OOC-Fc-COO)₃(2)，测定了两种配合物的晶体结构。配合物1中的金属铈离子为九配位结构，分别与周围的羧基二茂铁上的氧原子和作为辅助配体的水分子配位，茂铁间的π-π相互作用将配合物1的二聚体单元连结在一起形成二维的网状结构。配合物2中的金属铈离子亦为九配位结构，分别与周围的羧基二茂铁上的氧原子，作为辅助配体的水分子和甲醇配位形成类似于配合物1的二聚体单元，1，1′-二羧基二茂铁HOOC-Fc-COOH作为桥基配体将二聚体单元连结在一起，形成二维网状的配位聚合物。

Synthesis and Crystal Structures of Two New Ferrocenecarboxylato-Bridged Lanthanide Complexes

Two new ferrocenecarboxylato lanthanide complexes Ce2(FcCOO)6(H2O)4], 1 and Ce2(OOC-Fc-COO)3(H2O)3(CH3OH)] 2 have been synthesized and characterized by single-crystal X-ray crystallographic. In complex 1, two Ce(III) ions are bridged by two ferrocenecarboxylate anions as asymmetrically bridging ligands, leading to dimeric cores, each Ce(III) ion has an irregular polyhedral coordination environment with nine coordinated oxygen atoms derived from the ferrocenecarboxylate ligands and coordinated solvent molecules. Complex 2 is a two-dimensional network structure. Two types of coordination modes of ferrocenedicarboxylato(-2) ligands with different conformations are present in this structure. Each Ce(III) atom is in an eight coordination geometry bound by two oxygen atoms from two carboxylate groups of two antiperiplanar ferrocenedicarboxylato (-2), four oxygen atoms from three different carboxylate groups of two synperiplanar ligands and two oxygen atoms from two methanol molecules, respectively. CCDC: 248690, 248691.