The decomposition of formic acid catalysed by soluble metal complexes

Coffey, R. S.

doi:10.1039/c1967000923b

Cited by 65 publications

(59 citation statements)

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“…Few examples of this type of reaction were reported by Coffey, [11] Otsuka and co-workers, [12] Strauss et al, [13] and Trogler and co-workers, [14] who described the decomposition reaction with catalysts such as platinum, ruthenium, iridium, or rhodium complexes. Pd/C has also been used as a heterogeneous catalyst for the decomposition of formic acid and formate salts from 25 to 140 8C.…”

Section: Introductionmentioning

confidence: 91%

Hydrogen Generation at Ambient Conditions: Application in Fuel Cells

et al. 2008

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The efficient generation of hydrogen from formic acid/amine adducts at ambient temperature is demonstrated. The highest catalytic activity (TOF up to 3630 h(-1) after 20 min) was observed in the presence of in situ generated ruthenium phosphine catalysts. Compared to the previously known methods to generate hydrogen from liquid feedstocks, the systems presented here can be operated at room temperature without the need for any high-temperature reforming processes, and the hydrogen produced can then be directly used in fuel cells. A variety of Ru precursors and phosphine ligands were investigated for the decomposition of formic acid/amine adducts. These catalytic systems are particularly interesting for the generation of H2 for new applications in portable electric devices.

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Section: Introductionmentioning

confidence: 91%

Hydrogen Generation at Ambient Conditions: Application in Fuel Cells

et al. 2008

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“…IV showed absorptions at 1645 and 2225 m^ in the near IR (terminal hydrogens of the epoxy group) and a major fragmentation ion m/e = 59 caused by fission of the 2,3-C-C bond. Spectral data for I, II, III, and IV were identical with those re ported in the literature (34,36,37). When the reaction was run under conditions identical to those above in the absence of a metal complex or an initiator, less than 2% of oxidation products was observed (GLPC) after 4 hrs.…”

Section: Methodsmentioning

confidence: 92%

“…I, II, and IV were unaffected by column conditions while a small amount of decom position of III occurred in the injection port. For this reason, III was also analyzed titrimetrically [iodometric method (34) ] was obtained by preparative GLPC and identified by comparison of IR and NMR spectra with those of an authentic sample. Compound IV was obtained in > 99% purity by preparative GLPC and identified by comparison of its NMR spectrum with that given in the literature (36).…”

Section: Methodsmentioning

confidence: 99%

Oxidation of Olefins in the Presence of Transition Metal Complexes

Lyons

1974

Advances in Chemistry

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With certain metal complexes the product profile resulting from olefin oxidation differs greatly from that of classical autoxidation. Reactions carried out in the presence of cer tain metal complexes are highly selective in forming one product or a single set of products. When group VIII metal complexes are used, α,β unsaturated alcohols and ketones predominate. With molybdenum, epoxides are formed in high yield; with vanadium complexes, epoxy alcohols are formed. The oxidation of substituted olefins by the com plexes which we studied proceeds via an allylic hydroper oxide intermediate. The observed products are a function of the selective decomposition of the allylic hydroperoxide by the metal complex. In the decomposition of allylic hydroperoxides the products obtained with a given complex parallel the results of oxidation. Manytransition metal complexes react reversibly with molecular oxygen (1, 2) and with olefins (3, 4, 5). van Gaal et al. (6) recently prepared a group VIII metal complex which contains both oxygen and an olefin in the coordination sphere (Reaction 1).(1) L = PPh; PPh3 64

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“…However, an experimental proof has not been provided. [6] From technical perspective the observed activity of the Pt-and Pd-metal based catalyst systems is a good starting point for investigations on the reaction path and possible intermediates. To study the reaction path in detail by means of spectroscopic techniques, we synthesized a defined Pt hydrido complex as entry point for the catalysis and investigated its reaction with formic acid.…”

Section: Introductionmentioning

confidence: 99%

“…Besides metallic also molecular based catalyst systems containing platinum-group metals have been reported for the decomposition reaction of formic acid. [6][7][8][9][10][11] Many research efforts have been made to optimize the catalyst systems with regard to reaction parameters and cocatalysts. [10] However, despite these efforts little is known experimentally about intermediates and reaction steps of the catalytic decomposition of formic acid and the structure of the actual catalytically active species.…”

Section: Introductionmentioning

confidence: 99%

Platinum Complex Catalyzed Decomposition of Formic Acid

et al. 2010

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Keywords: Platinum / Hydride ligands / Hydrogen storage / C-H activation / Ab initio calculations / Homogeneous catalysis / Formic acid decompositionThe decomposition of formic acid catalyzed by a cationic hydridoplatinum tetradentate phosphane complex was studied by NMR spectroscopy, isotope labeling and DFT calculations.In the initial step dihydrogen is formed by the reaction of the formic acid with the hydrido ligand yielding a platinum formate cation. The formato ligand is then transformed to CO 2 by a β-H transfer of the formate C-H bond to the Pt center revealing the initial cationic Pt-H complex. The reaction sequence was illuminated by deuterium and C-13 isotope labeling revealing the cationic Pt-D complex as only Pt

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The decomposition of formic acid catalysed by soluble metal complexes

Cited by 65 publications

References 0 publications

Hydrogen Generation at Ambient Conditions: Application in Fuel Cells

Hydrogen Generation at Ambient Conditions: Application in Fuel Cells

Oxidation of Olefins in the Presence of Transition Metal Complexes

Platinum Complex Catalyzed Decomposition of Formic Acid

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