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 CO2 and H2) 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.
A novel methodology is presented for the direct methylation of amines, using formic acid as a unique source of carbon and hydrogen. Based on ruthenium(II) catalysts, the formation of the N-CH3 group proceeds via an efficient formylation/transfer hydrogenation pathway.
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