Extraordinary coordination of acetonitrile to square-planar, 1,4,8,11-tetraazacyclotetradecanenickel(II) and (1R,4R,8S,11S)-1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecanenickel(II) cations.
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概要
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Coordination of dipolar aprotic solvents to the square-planar complexes of nickel(II) was investigated in nitrobenzene (NB) spectrophotometrically. Compared with <I>N</I>,<I>N</I>-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), it was observed that acetonitrile (AN) was strongly coordinated to [NiL]<SUP>2+</SUP> (L=1,4,8,11-tetramethyl-1,4,8,ll-tetraazacyclotetradecane). The stepwise coordination constants <I>K</I><SUB>NiS1</SUB> and <I>K</I><SUB>NiS2</SUB> (mol<SUP>−1</SUP> dm<SUP>3</SUP>) for (1<I>R</I>,4<I>R</I>,8<I>S</I>,11<I>S</I>)-[NiL]<SUP>2+</SUP> were found to be (1.6, 0.5), (1.0, 0.1), (3.4, 6.7), and (0.4, 1.9) for DMSO, DMF, AN, and benzonitrile, respectively. The <I>K</I><SUB>NiS2</SUB> values for nitriles are larger than the <I>K</I><SUB>NiS1</SUB> values, showing that nitriles are coordinated to the metal ion through π-back donation.
著者
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Yokoyama Takashi
Department Of Chemistry Faculty Of Science Kyushu University
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Kumamaru Takahiro
Department Of Chemistry Faculty Of Science Hiroshima University
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KUMAMARU TAKAHIRO
Department of Chemistry, Faculty of Science, Hiroshima University
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Iwamoto Etsuro
Department of Chemistry, Faculty of Science, Hiroshima University
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