The effects of multivalent anions on the aluminium ion-assisted aquation of the pentaamminefluorocobalt(III) complex.

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概要

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• The presence of multivalent anions, such as sulfate, oxalate, and malonate ions, accelerated the aluminium ion-assisted aquation of CoF(NH<SUB>3</SUB>)<SUB>5</SUB><SUP>2+</SUP> and gave the anionopentaamminecobalt(III), along with the aqua complex. The competition reaction for the sulfate ion showed a saturation of the product percentage (33% CoSO<SUB>4</SUB>(NH<SUB>3</SUB>)<SUB>5</SUB><SUP>+</SUP>) at nearly [SO<SUB>4</SUB><SUP>2−</SUP>]<SUB>total</SUB>=0.1 mol dm<SUP>−3</SUP>, while the saturation of the reaction rate was observed at a higher sulfate concentration. This difference can be explained by a scheme in which the reaction proceeds through two intermediates, CoF(NH<SUB>3</SUB>)<SUB>5</SUB><SUP>2+</SUP>·SO<SUB>4</SUB><SUP>2−</SUP>·Al<SUP>3+</SUP> and SO<SUB>4</SUB><SUP>2−</SUP>·CoF(NH<SUB>3</SUB>)<SUB>5</SUB><SUP>2+</SUP>·SO<SUB>4</SUB><SUP>2−</SUP>·Al<SUP>3+</SUP>. The reaction for the oxalate and malonate ions gave extremely large yields (more than 90%) of CoA(NH<SUB>3</SUB>)<SUB>5</SUB><SUP>+</SUP> (A<SUP>2−</SUP>=oxalate ion or malonate ion) when [A<SUP>2−</SUP>]<SUB>total</SUB>/[Al<SUP>3+</SUP>]<SUB>total</SUB>>2, and the reaction rates showed a maximum at approximately [A<SUP>2−</SUP>]<SUB>total</SUB>/[Al<SUP>3+</SUP>]<SUB>total</SUB>=2. These specific effects can be attributed both to the strong affinities of the dicarboxylate ions for the aluminium ion and to the residual capacity of the aluminium-bonded dicarboxylate ions for coordinating with cobalt(III).

• 公益社団法人 日本化学会の論文

著者

• Iida Masayasu

  Department Of Chemistry Faculty Of Science Nara Women's University

• Yamatera Hideo

  Department of Chemistry, Faculty of Science, Nagoya University

• Ando Mieko

  Department of Chemistry, Faculty of Science, Nara Women's University

• Ando Mieko

  Department of Chemistry, Faculty of Science, Nara Women's University

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