非水溶媒中における白金族錯体の電気化学的研究　Os (II) および Ru (II)－αα'－ビピリジンと類縁錯体の電気化学的挙動

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  • 非水溶媒中における白金族錯体の電気化学的研究--Os(2)およびRu(2)-αα′-ビピリジンと類縁錯体の電気化学的挙動
  • ヒスイ ヨウバイチュウ ニ オケル ハッキンゾク サクタイ ノ デンキ カガク
  • The Electrochemical Study of Platinum Metal Complexes　　The Electrochemical Behaviour of Os (II) and Ru (II) Complexes with αα'-Bipyridine and o-Phenanthlorine in Non Aqueous Solvents

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Electrochemical behaviours of Os (II)-αα'-bipyridine, Os (II)-o-phenanthroline, and Ru (Il)-αα' bipyridine complexes are studied in non aqueous solvents. An electrode reaction of tris-complex consists of three reversible one-electron reduction processes and a reversible one-electron oxidation process. While an electrode reaction of bis bipyridine complex (one of three bipyridine ligands is replaced by other ligands such as py2, CN2 and en, etc.) consists of two reversible one-electron reduction processes and a reversible one-electron oxidation process. In bis-bipyridine complexes, half-wave potentials (and peak potentials) depend also on ligands such as py2, CN2 and en. Both oxidation and reduction potentials of the bis-complexes shift towards negative direction from potentials of the tris-complex. Among isoelectronic complexes : Os(bip)32+, Os(bip)2(py)22+ and Os(en)(bip)22+, tbe extent of the of shift is in the order bip<py<en, while for Os(bip)2(CN)2, Os(bip)2(Cl)2 and Os(bip)2(Br)2, the order is CN-<Cl-<Br-.In the oxidation process the shift also depends on a central atom and the order of influence is Os<Ru <Fe. An electron is removed from d orbital of a central atom at the electrode reaction and d5 complex is formed. In the reduction process the shifts scarcely depend on a central atom, because electrons are added to π*-orbital of ligands so that a central atom does not exert influence. The experimental result that reduction potentials depend on ligands such as py2, CN2 and en, suggests, however, that these ligands can exert influences on bipyridine ligand probably through central atom.

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