Spin-state equilibria of the nickel(II) complexes of 2,12-dimethyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),2,11,13,15-pentaene analogs in water.

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概要

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• Spin-state equilibria between a singlet low-spin and a triplet high-spin species of the title complexes in water were investigated by means of electronic spectra. The equilibrium constants and the thermodynamic parameters, Δ<I>H</I> and Δ<I>S</I>, were evaluated from detailed analysis of the temperature-dependence of the electronic spectra. The electronic spectra of the singlet and the triplet species involved were also derived, from the same analysis. The formation of the triplet species was found to be exothermic, which reflects the predominant contribution of the exothermic change to the formation of nickel(II)–water bond over the contribution of the endothermic change in the bond length caused by the change in spin state. The absolute values of Δ<I>S</I> almost correspond to those expected for the effective liberation of two molecules of water in aqueous solution.

• 公益社団法人 日本化学会の論文

著者

• Mochizuki Katsura

  Department Of Chemistry Faclty Of Science And Graduate School Of Integrated Science Yokohama City Un

• Ito Tasuku

  Institute For Molecular Science

• FUJIMOTO Masatoshi

  Department of Chemistry, Faculty of Science, Hokkaido University

• Ito Haruko

  Institute for Molecular Science

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