Efficient Disproportionation of Formic Acid to Methanol Using Molecular Ruthenium Catalysts

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 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.

An active, stable and recyclable Ru(ii) tetraphosphine-based catalytic system for hydrogen production by selective formic acid dehydrogenation

“…In the case of complex 1, a higher TOF 10min = 1868 h -1 was obtained for the both first and second runs (entry 13). The same behavior was observed for 2 and 3, with TOF 10min of 2687 and 2866 h -1 , respectively (entries 14,15). We were interested to evaluate the possible activity of our complexes for FA DH in absence of base, which has been rarely described in the case of Ru complexes.…”

Catalytic Disproportionation of Formic Acid to Methanol by an Iridium Complex Immobilized on Bipyridine‐Periodic Mesoporous Organosilica

“…[10] Recently, Himeda et al achieved a significant improvement in MeOH selectivity using [IrCp*(dmbp)(H 2 O)](SO 4 ) (dmbp = 5,5'-dimethyl-2,2'-bipyridine) under pressurized H 2 conditions (e. g., pressurized H 2 , ligand modification, and addition of H 2 SO 4 ; selectivity: 47.1 %). [12] These studies show that a high pressure condition in a closed system and an addition of acid are important to improve the MeOH selectivity. [12] These studies show that a high pressure condition in a closed system and an addition of acid are important to improve the MeOH selectivity.…”

Carbon Dioxide to Methanol: The Aqueous Catalytic Way at Room Temperature

“…[3,4] In addition, both FA and MeOH may be utilizeda se asy-to-handle H 2 storagem edia. [15][16][17] To date, the bestr esultsf or the FA disproportionation reactionr eport aM eOH yield of 50 %( with 50 %c ompeting dehydrogenation) in THF at 150 8C, in the presence of aruthenium-phosphine catalyst andamethanesulfonic acid additive. [6] In recent years, an umber of groups has investigated the conversion of CO 2 derivatives or CO 2 to methanoli nt he presence of homogeneous catalysts.…”