Bridges in polynuclear complexes. II. An X-ray investigation of the coordination of silver ion to the .MU.-peroxo bridge of a dinuclear Cobalt(III) complex.

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概要

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• The crystal structure of [(en)<SUB>2</SUB>Co(NH<SUB>2</SUB>)(O<SUB>2</SUB>)Co(en)<SUB>2</SUB>](NO<SUB>3</SUB>)<SUB>3</SUB>·15/8(AgNO<SUB>3</SUB>)·H<SUB>2</SUB>O has been determined from X-ray diffraction data collected by the counter method. The crystal is monoclinic with the space group C2/c and with <I>a</I>=8.710(3), <I>b</I>=16.413(5), <I>c</I>=20.024(8)Å, β=90.30(4)°, and <I>Z</I>=4. The structure was refined by the block-diagonal least-squares method to <I>R</I>=0.107 for 2157 independent reflections. It has been elucidated that the Ag atom is bound to each of the two peroxo oxygen atoms with the Ag–O bond length of 2.27(1) Å. Each Ag atom is also surrounded by two more oxygen atoms belonging to the nitrate anions and these Ag–O bond lengths are 2.45(2) and 2.50(2) Å. The central five-membered ring has a symmetric envelope conformation, with the peroxo O atom deviating from the Co, N, Co plane, by 0.38 Å. The crystals contain an equal amounts of the enantiomeric forms (<SUP>δ</SUP><SUB>δ</SUB>Λδ<SUP>δ</SUP><SUB>δ</SUB>) and (<SUP>λ</SUP><SUB>λ</SUB>ΔλΔ<SUP>λ</SUP><SUB>λ</SUB>). The formation constant of Ag<SUP>+</SUP> and [(en)<SUB>2</SUB>Co(NH<SUB>2</SUB>)(O<SUB>2</SUB>)Co(en)<SUB>2</SUB>]<SUP>3+</SUP> in aqueous solution was found to be less than 0.5.

• 公益社団法人 日本化学会の論文

著者

• Matsumoto Keiji

  Department Of Applied Physics Graduate School Of Engineering Yokohama National University

• Shibahara Takashi

  Department Of Chemistry Faculty Of Science Okayama University Of Science

• Mori Masayasu

  Department of Chemistry, Faculty of Science, Osaka City University

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