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

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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.