Kinetic study of oxidative addition and replacement reactions of chlorotris(triphenylphosphine)rhodium(I) in benzene.

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概要

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• Chlorotris(triphenylphosphine)rhodium (I) exists in benzene as RhCl(PPh<SUB>3</SUB>)<SUB>3</SUB>, a dimeric species [RhCl(PPh<SUB>3</SUB>)<SUB>2</SUB>]<SUB>2</SUB> and a reaction intermediate RhCl(PPh<SUB>3</SUB>)<SUB>2</SUB>. The rates of oxidative addition and replacement reactions were examined in benzene. For the oxidative addition reaction, RhCl(PPh<SUB>3</SUB>)<SUB>3</SUB>, RhCl(PPh<SUB>3</SUB>)<SUB>2</SUB>, or [RhCl(PPh<SUB>3</SUB>)<SUB>2</SUB>]<SUB>2</SUB>+X<SUB>1</SUB>\overset<I>k</I><SUB>add</SUB>\rightleftarrowsProducts (X<SUB>1</SUB>=H<SUB>2</SUB>, O<SUB>2</SUB>, C<SUB>2</SUB>H<SUB>4</SUB>, CHCl=CCl<SUB>2</SUB> CH<SUB>3</SUB>I), it was found that the reaction intermediate RhCl(PPh<SUB>3</SUB>)<SUB>2</SUB> is most reactive, the degree of its reactivity depending largely on the reactants (X<SUB>1</SUB>). A significant enhancement of the rate (<I>k</I><SUB>sub</SUB>><I>k</I><SUB>add</SUB>) was observed for the ligand substitution reaction, RhClX<SUB>1</SUB>(PPh<SUB>3</SUB>)<I><SUB>m</SUB></I>+X<SUB>2</SUB>\overset<I>k</I><SUB>sub</SUB>\rightleftarrowsRhClX<SUB>2</SUB>(PPh<SUB>3</SUB>)<I><SUB>n</SUB></I>+X<SUB>1</SUB> (<I>m</I>, <I>n</I>=3 or 2), where X<SUB>1</SUB>=H<SUB>2</SUB> and X<SUB>2</SUB>=olefin and <I>vice versa</I>. The results are discussed in relation to the mechanism of hydrogenation.

• 公益社団法人 日本化学会の論文

著者

• Yamagishi Akihiko

  Department Of Chemistry College Of Arts And Sciences The University Of Tokyo

• FUJIMOTO Masatoshi

  Department of Chemistry, Faculty of Science, Hokkaido University

• Ohtani Yoshimi

  Department of Chemistry, Faculty of Science, Hokkaido University

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