Substituent effects in heterogeneous catalysis. III. Competitive hydrogenation of cyclohexanone and 2-alkylcyclohexanones over platinum group metals.
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Cyclohexanone (<B>1</B>) and one of its 2-alkyl (methyl, ethyl, or propyl) derivatives (<B>2</B>) were hydrogenated competitively at 30 °C in cyclohexane over platinum group metals. The alkyl derivatives <B>2</B> were all less reactive than <B>1</B> on all the catalysts used. The relative reactivity <I>R</I><SUB>2</SUB>⁄<I>R</I><SUB>1</SUB> was given by log<SUB>10</SUB>(<I>R</I><SUB>2</SUB>⁄<I>R</I><SUB>1</SUB>)=σ<SUP>**</SUP>+<I>k</I>, with σ<SUP>**</SUP> depending only upon the substituent and <I>k</I> upon the catalyst. The greater the substituent size, the more negative was the substituent constant σ<SUP>**</SUP>. The catalyst-dependent constant <I>K</I> was in general more negative for a catalyst metal having a smaller atomic radius. The above empirical rate expression has been interpreted based on the absolute reaction rate theory. The σ<SUP>**</SUP> values calculated on this theoretical ground were in excellent agreement with the observed values.
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