Hydrogenation of carbon dioxide to formic acid using water-soluble rhodium catalyststs

Abstract

Water-soluble rhodium-phosphane complexes are very efficient catalysts for the hydrogenation of carbon dioxide to formic acid in water-amine mixtures similar to those used for separation of C02 from flue gases.

A Well‐Defined Iron Catalyst for the Reduction of Bicarbonates and Carbon Dioxide to Formates, Alkyl Formates, and Formamides

“…Based on our previous studies on the ruthenium-catalyzed hydrogenation of carbonate and bicarbonate, [15] we describe herein for the first time an active iron catalyst system which can be used for the reduction of both carbon dioxide and bicarbonates to give formates, alkyl formates, and formamides. Central to the success of this work is the combination of the iron source Fe(BF 4 (6) under the reaction conditions.…”

“…One promising approach to overcoming the low reactivity of CO 2 [1] is its activation by catalytic hydrogenation to form formic acid or its derivatives. [2] Until now, noble-metal catalysts based on rhodium, [3,4] ruthenium, [5][6][7] and iridium [8,9] were mostly used for this transformation. Graf and Leitner had already achieved significant turnover numbers (TONs) of 3400 with rhodium phosphine complexes in the early 1990s.…”

Arene ruthenium oxinato complexes: Synthesis, molecular structure and catalytic activity for the hydrogenation of carbon dioxide in aqueous solution

“…This reaction, first reported in 1976 by Inoue and co-workers, is catalyzed by various group VIII metal phosphine complexes in benzene in the presence of water and base [23]. The direct formation of formic acid from CO 2 and H 2 in supercritical carbon dioxide using ruthenium catalysts was pioneered by Noyori and Jessop [24][25][26][27][28], while the hydrogenation of carbon dioxide in water, catalyzed by watersoluble rhodium or ruthenium complexes was developed by Gassner and Leitner [29] and by Joó and Laurenczy [30][31][32][33]. Himeda carefully studied the influence of the pH on this reaction and designed rhodium, iridium and ruthenium complexes containing chelating N,N-ligands that can be deprotonated and that are highly active in basic solution [34].…”

Ruthenium‐Catalyzed Hydrogenation of Bicarbonate in Water

“…HCO 2 H Since the early 1990s significant advances towards the hydrogenation of CO 2 to formic acid, or its salt, by applying complexes of transition metals such as rhodium, [4,5] ruthenium, [6][7][8] and iridium [9,10] have been described. [3] More specifically, in 1993 Leitner et al achieved a catalyst turnover number (TON) of 3400 for the hydrogenation of CO 2 to formic acid with Rh phosphine complexes at room temperature.…”