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Efficient Disproportionation of Formic Acid to Methanol Using Molecular Ruthenium Catalysts
Author(s) -
Savourey Solène,
Lefèvre Guillaume,
Berthet JeanClaude,
Thuéry Pierre,
Genre Caroline,
Cantat Thibault
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201405457
Subject(s) - formic acid , disproportionation , methanol , ruthenium , dehydrogenation , catalysis , chemistry , yield (engineering) , phosphine , iridium , photochemistry , inorganic chemistry , organic chemistry , materials science , metallurgy
Abstract The disproportionation of formic acid to methanol was unveiled in 2013 using iridium catalysts. Although attractive, this transformation suffers from very low yields; methanol was produced in less than 2 % yield, because the competitive dehydrogenation of formic acid (to CO 2 and H 2 ) is favored. We report herein the efficient and selective conversion of HCOOH to methanol in 50 % yield, utilizing ruthenium(II) phosphine complexes under mild conditions. Experimental and theoretical (DFT) results show that different convergent pathways are involved in the production of methanol, depending on the nature of the catalyst. Reaction intermediates have been isolated and fully characterized and the reaction chemistry of the resulting ruthenium complexes has been studied.