Stereoselective association between acetylacetonatobis(ethylenediamine)cobalt(III) and malonate ions as studied by nuclear magnetic resonance.

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概要

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• The effect of added malonate upon the chemical shift and the exchange rate of amine hydrogens of acetylacetonatobis(ethylenediamine)cobalt(III) ion, [Co(acac)(en)<SUB>2</SUB>]<SUP>2+</SUP>, have been investigated by <SUP>1</SUP>H and <SUP>13</SUP>C NMR spectroscopy. In the absence of malonate, the amine groups give rise to two signals in the <SUP>1</SUP>H spectra and two rate constants of amine exchange due to <I>trans</I> and <I>cis</I> (to coordinated oxygen) amine groups. Upon addition of malonate, the <I>trans</I> NH<SUB>2</SUB> undergoes a down-field shift, the <I>cis</I> NH<SUB>2</SUB> resonance splitting into two peaks. In the presence of malonate, all of the four kinds of amine hydrogens of [Co(acac)(en)<SUB>2</SUB>]<SUP>2+</SUP> exhibit different exchange rates. The following conclusion was obtained from the results coupled with <SUP>13</SUP>C NMR data, (i) The malonate ion works in two ways in amine exchange, as a general base catalyst and to form an exchange-inert ion-pair, (ii) The two <I>trans</I> hydrogens that are directed approximately parallel to the two-fold axis of the complex ion hydrogen-bond simultaneously to the two carboxyl groups of malonate, leading to a retardation of amine exchange rates. (iii) The rates of the other <I>trans</I> hydrogens and <I>cis</I> hydrogens are determined by a compromise between acceleration due to general base catalysis and deceleration due to forming ion-associated species, (iv) The conformation of coordinated ethylenediamine is fixed as either (δδ) or (λλ) in the hydrogen-bonded species.

• 公益社団法人 日本化学会の論文

著者

• YONEDA Hayami

  Department of Chemistry, Faculty of Science, Hiroshima University

• Nakazawa Hiroshi

  Department Of Applied Biology Faculty Of Textile Science Kyoto Institute Of Technology

• Sakaguchi Ushio

  Department of Chemistry, Faculty of Science, Hiroshima University

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