The Kinetics and Mechanisms of Reaction of Iodine with Bis(<I>N</I>,<I>N</I>-diethyldithiocarbamato)dimethyltin(IV) and Related Compounds
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概要
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The reactions of Me<SUB>2</SUB>SnL(S<SUB>2</SUB>CNEt<SUB>2</SUB>) (L=S<SUB>2</SUB>CNEt<SUB>2</SUB> (<B>1</B>) and I (<B>2</B>)) with iodine in cyclohexane were investigated employing a stopped-flow technique. The kinetic data indicate that the reaction in the presence of a large excess of <B>1</B> or <B>2</B> proceeds <I>via</I> a charge-transfer complex of Me<SUB>2</SUB>SnL(S<SUB>2</SUB>CNEt<SUB>2</SUB>)·I<SUB>2</SUB>, which decomposes in the ratedetermining step to yield Me<SUB>2</SUB>SnI(L) and unstable I(S<SUB>2</SUB>CNEt<SUB>2</SUB>). This unstable intermediate reacts with the excess <B>1</B> or <B>2</B> to afford Me<SUB>2</SUB>SnI(L) and tetraethylthiuramdisulfide (<B>3</B>). The reaction of <B>1</B> with a large excess of I<SUB>2</SUB>was also kinetically studied to reveal the formation of the 1 : 2 complex, Me<SUB>2</SUB>Sn(S<SUB>2</SUB>CNEt<SUB>2</SUB>)<SUB>2</SUB>·2I<SUB>2</SUB>, as an intermediate; this intermediate then undergoes a simultaneous degradation to afford Me<SUB>2</SUB>SnI<SUB>2</SUB> and <B>3</B>. The transition state in the reaction is discussed.
- 公益社団法人 日本化学会の論文
著者
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Tanaka Koji
Department Of 1st Internal Medicine Osaka Medical College
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Kita Hidetoshi
Department of Advanced Materials Science & Engineering, Faculty of Engineering, Yamaguchi University
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Tanaka Toshio
Department of Applied Chemistry, Faculty of Engineering, Osaka Univeristy
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Tanaka Koji
Department of Applied Chemistry, Faculty of Engineering, Osaka University
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