A study of trans influence in methylmercury(II) compounds by means of vibrational analysis.
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概要
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Force constants <I>K</I>(Hg–C) were evaluated for a series of methylmercury compounds: CH<SUB>3</SUB>HgX (X=CH<SUB>3</SUB>, F, Cl, Br, I, CN, SCN, As(CH<SUB>3</SUB>)<SUB>3</SUB>, SCH<SUB>3</SUB>, SHgCH<SUB>3</SUB>, and S(HgCH<SUB>3</SUB>)<SUB>2</SUB>). It was found that <I>K</I>(Hg–C) increases in the following order of X: S(HgCH<SUB>3</SUB>)<SUB>2</SUB>(1.86)<I(2.27)<SCH<SUB>3</SUB>(2.33)=CH<SUB>3</SUB>(2.330)<As(CH<SUB>3</SUB>)<SUB>3</SUB>(2.37)≤Br(2.37<SUB>7</SUB>)≤SHgCH<SUB>3</SUB>(2.38)≤Cl(2.38<SUB>2</SUB>)<SCN(2.39)<F(2.55)<CN(2.61 md/Å). This order coincides, except for the cases of CN and As(CH<SUB>3</SUB>)<SUB>3</SUB>, with the order of increase in the first ionization potential of X for X=I, SCH<SUB>3</SUB>, CH<SUB>3</SUB>, Br, Cl, and F. Since this effect of X upon <I>K</I>(Hg–C) is regarded as a vibrational <I>trans</I> influence, this order was compared with that of the coupling constants in NMR, <I>J</I>(<SUP>199</SUP>Hg–<SUP>13</SUP>C) and <I>J</I>(<SUP>199</SUP>Hg–<SUP>1</SUP>H), and with the order of the bond-dissociation energy of CH<SUB>3</SUB>HgX into ·CH<SUB>3</SUB> and ·HgX.
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