Ralf Haiges - Formic Acid As a Hydrogen Storage Medium: Ruthenium-Catalyzed Generation of Hydrogen from Formic Acid in Emulsions.

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      Publication Details (including relevant citation   information): Czaun, Miklos, Goeppert, Alain,   Kothandaraman, Jotheeswari, May, Robert B., Haiges, Ralf,   Prakash, G. K. Surya, Olah, George A., ACS Catal.,   2014, 4 (1), pp 311-320

      Abstract: Formic acid is decompd. to H2 and CO2   in the presence of RuCl3 and triphenylphosphines in an emulsion.   In situ formed ruthenium carbonyls, such as   [Ru(HCO2)2(CO)2(PPh3)2] (1), [Ru(CO)3(PPh3)2] (2), and   [Ru2(HCO2)2(CO)4(PPh3)2] (3), and a large cluster, involving a   Ru12 core, were identified and structurally characterized from   the reaction mixts. The catalytic activity of the mono and   binuclear complexes was also investigated and   [Ru2(HCO2)2(CO)4(PPh3)2] (3) shows high stability even at   elevated temps. and pressures and its activity is 1 order of   magnitude lower than those measured for the mononuclear   complexes. It was also attempted to use [Ru(HCO2)2(CO)2(PPh3)2]   (1) as a catalyst for the hydrogenation of CO2 to formic acid   under neutral conditions. Although the redn. of CO2 did not take   place, the conversion of [Ru(HCO2)2(CO)2(PPh3)2] (1) to an   unexpected carbonate, [Ru(CO3)(CO)2(PPh3)2]·H2O was obsd. [on   SciFinder(R)]

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