Inversion at selenium in (MIII(RSeCH2CH2NH2){N(CH2CH2NH2)3})3+(MIII=Co,Rh; R=CH3,CH3CH2,C6H5CH2) and (Co(CH3SeCH2COO){N(CH2CH2NH2)3})2+.

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概要

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• The selenoether (selenide) complexes, <I>t</I>-[Co(RSeCH<SUB>2</SUB>CH<SUB>2</SUB>NH<SUB>2</SUB>)(tren)]<SUP>3+</SUP> (<I>t</I>=<I>trans</I>(<I>tertiary amine nitrogen</I>, <I>Se</I>); R=CH<SUB>3</SUB>, CH<SUB>3</SUB>CH<SUB>2</SUB>, C<SUB>6</SUB>H<SUB>5</SUB>CH<SUB>2</SUB>; tren=tris(2-aminoethyl)amine), <I>p</I>-[Rh(CH<SUB>3</SUB>SeCH<SUB>2</SUB>CH<SUB>2</SUB>NH<SUB>2</SUB>)(tren)]<SUP>3+</SUP> (<I>p</I>=<I>cis</I>-(<I>tertiary amine nitrogen</I>, <I>Se</I>)), and <I>t</I>-[Co(CH<SUB>3</SUB>SeCH<SUB>2</SUB>COO)(tren)]<SUP>2+</SUP> were prepared and resolved for the first time by the chemical or SP-Sephadex column chromatographic method. Racemization of these complexes in aqueous solutions was studied at an ionic strength of 0.25 (NaClO<SUB>4</SUB>) in the pH and temperature ranges of 4.00–6.91 and 0.25–33.50 °C, respectively. The racemization rates were independent of pH and an intramolecular inversion mechanism was suggested. The Δ<I>G</I><SUB>25°C</SUB><SUP>\neweq</SUP> values for inversion of <I>t</I>-[Co(RSeCH<SUB>2</SUB>CH<SUB>2</SUB>NH<SUB>2</SUB>)(tren)]<SUP>3+</SUP> decreases in the order of CH<SUB>3</SUB> (95.2 kJ mol<SUP>−1</SUP>)>CH<SUB>3</SUB>CH<SUB>2</SUB> (89.4)>C<SUB>6</SUB>H<SUB>5</SUB>CH<SUB>2</SUB> (87.7), while the Δ<I>H</I><SUP>\neweq</SUP> values are almost the same (95–97 kJ mol<SUP>−1</SUP>). The variable-temperature <SUP>13</SUP>C NMR study of <I>p</I>-[Co(CH<SUB>3</SUB>SeCH<SUB>2</SUB>CH<SUB>2</SUB>NH<SUB>2</SUB>)(tren)]<SUP>3+</SUP> yielded the inversion rate constant, 10 s<SUP>−1</SUP> at the coalescence temperature (<I>ca.</I> 60 °C), which is much larger than that of the corresponding <I>t</I>-isomer (8.5×10<SUP>−3</SUP>s<SUP>−1</SUP> at 60 °C). The difference in inversion rate between the isomers seems to be related to the steric crowding around the Se-R group of the complex. The rhodium(III) complex racemizes slower than the corresponding cobalt(III) complex. The values of thermodynamic parameters for <I>t</I>-[Co(CH<SUB>3</SUB>SeCH<SUB>2</SUB>COO)(tren)]<SUP>+2</SUP> are nearly the same as those for <I>t</I>-[Co(CH<SUB>3</SUB>SeCH<SUB>2</SUB>CH<SUB>2</SUB>NH<SUB>2</SUB>)(tren)]<SUP>3+</SUP>.

• 公益社団法人 日本化学会の論文

著者

• Nakajima Kiyohiko

  Department Of Chemistry Aichi University Of Education

• Kojima Masaaki

  Department Of Chemistry Faculty Of Science Okayama University

• Fujita Junnosuke

  Department of Chemistry Faculty of Science Osaka University

• Nakajima Kiyohiko

  Department of Chemistry, Faculty of Science, Nagoya University

• Tozaki Katsuhiko

  Department of Chemistry, Faculty of Science, Nagoya University

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