Deuteration reaction of malonate hydrogens in some monomalonatocobalt(III) compounds.
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概要
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The rate of deuteration at malonate hydrogens has been measured for [Co(mal)(N)<SUB>4</SUB>]<SUP>+</SUP> and [Co(malH)(NH<SUB>3</SUB>)<SUB>5</SUB>]<SUP>2+</SUP> ions in aqueous solution over the pD range of 2 to 8, where mal=malonate dianion, malH=malonate monoanion, and (N)<SUB>4</SUB>=(NH<SUB>3</SUB>)<SUB>4</SUB>, (ethylenediamine)<SUB>2</SUB>, (1,3-propanediamine)<SUB>2</SUB>, (1,10-phenanthroline)<SUB>2</SUB>, or (2,2′-bipyridine)<SUB>2</SUB>. For the tetraamine type complexes with a chelated malonate ligand, the deuteration process is acid-catalysed up to pD=about 4 and base-catalysed at higher pD values. This contrasts with the behavior of the unidentate malonate ligand, for which the deuteration is base-catalysed up to pD=3.5, whereupon the deprotonation of the carboxylate group takes place and the deuteration rate steps down to a constant, pH-independent value. The deuteration mechanisms are discussed.
- 公益社団法人 日本化学会の論文
著者
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YONEDA Hayami
Department of Chemistry, Faculty of Science, Hiroshima University
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Sakaguchi Ushio
Department of Chemistry, Faculty of Science, Hiroshima University
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Nakano Michie
Department of Chemistry, Faculty of Science, Hiroshima University
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