Stereochemistry of alkyl pendant ligands coordinated to metal complexes and its effect on reactivity

合成了含烷基侧链配体的钴、铁、铂配合物，并阐明了它们的性质。N-烷基取代基[Co^&lt；III&gt；(CN)_4L]^&lt；3+&gt；或[Co^&lt；III&gt；(NH_3)_4L]^&lt；3+&gt；(L=Eten或Be)在查尔环和反构象方面呈假赤道配置。在水溶液中，[Pt(Bpy)L]^&lt；2+&gt；和[Pt(Bpy)L]^&lt；2+&gt；的N-苄基发生了假轴配置，芳环之间发生了分子内疏水相互作用。以N-萘甲基和N-苯甲甲基取代N-苄基，增强了分子内相互作用。在水溶液和晶体中，悬浮体均呈-SYN-构象，分子力学计算支持该构象。非极性溶剂或蛋白质变性剂如尿素的加入减弱了这些复合体的分子内疏水相互作用。[Fe^&lt；II&gt；(CN)_4(Be)]用H_2O_2氧化生成单亚胺和双亚胺络合物。这是由于仲胺的反应活性增强所致。利用该脱氢反应首次从二胺络合物中分离得到了单亚胺络合物。随着亚甲基桥(N)数1~5的变化，联吡二胺与N-omega-苯基烷基乙二胺配合物中芳环间的分子内相互作用随着n=1的变化而最强。当n=3时，这些配合物与芳香磺酸盐的分子间相互作用最强。

The Co, Fe, and Pt complexes containing the alkyl pendant ligands were synthesized and their characteristics were clarified.1. N-Alkyl substituents of [Co^<III>(CN)_4L]^<3+> or [Co^<III>(NH_3)_4L]^<3+>(L=Eten or Been) took pseudoequatorial disposition in regard with the chalete ring and anti-conformation. N-Benzyl group of [Pt(bpy)L]^<2+> and [Pt(bpy)L]^<2+> took pseudoaxial disposition and a intramolecular hydrophobic interaction occurred between the aromatic rings in aqueous solution. Substitution of N-benzyl with N-naphthylmethyl and N-anthrylmethyl in the ternary Pt^<II> enhanced the intramolecular interaction. In both aqueous solution and crystals, the pendants took -syn -conformation which was supported by a molecular mechanics calculation. Intramolecular hydrophobic interaction of these complexes were weakened by addition of nonpolar solvents or protein denaturants such as urea.2. The oxidation of [Fe^<II>(CN)_4(Been)] with H_2O_2 yielded consecutively the monoimine and the diimine complexes. This was due to the enhanced reactivity at the secondary amine. The monoimine complex was isolated for the first time from the diamine complex by using this dehydrogenation.3. Intramolecular interaction between aromatic rings in Pt^<II> complexes of bpy and N-omega-phenyl-alkylethylenediamine with variation of the number of methylene brige(n) 1 to 5, was most strengthened with n=1. The intermolecular interaction between these complexes and aromatic sulfonate was most strengthened with n=3.