"Ruthenium Promoted Radical Processes Toward Fine Chemistry"

Lionel Delaude, Albert Demonceau, and Alfred F. Noels

book cover
           title: Ruthenium Catalysts and Fine Chemistry
          series: Topics in Organometallic Chemistry
         editors: Christian Bruneau and Pierre H. Dixneuf
       publisher: Springer
            city: Berlin
            year: 2004
          volume: 11
      first page: 155
       last page: 171
            isbn: 3-540-20543-8
             doi: 10.1007/b94645

Abstract: Ruthenium holds a prominent position among the many transition metals used in radical chemistry. The dichlorotris(triphenylphosphine) complex [RuCl2(PPh3)3] was the first active ruthenium-based catalyst investigated for atom-transfer radical addition processes and has found numerous applications in organic synthesis. Other catalytic systems that have been devised since include (1) neutral or cationic Grubbs-type complexes bearing an alkylidene fragment and either phosphine, N-heterocyclic carbene, or Schiff base ligands; (2) half-sandwich ruthenium complexes bearing a cyclopentadienyl, a pentamethylcyclopentadienyl, or an indenyl ligand, and (3) ruthenium complexes bearing anionic carborane-phosphine and dicarbollide ligands. Their activities are discussed and the predictive value of cyclic voltammetry in radical chemistry is questioned. A related example of a ruthenium-catalyzed C-H hydroxylation reaction is also reported.

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