Facile hydrogen-transfer reduction of multiple bonds by formic acid catalysed with a Pd-561 giant cluster

Reaction between palladium(II) and gallium(III) halogenides in arenes: influence of halogen nature on the formation of binuclear palladium(I) clusters

“…The structure, chemistry and catalytic properties of clusters with Pd-Pd bonds were recently reviewed [2,3]. These compounds take part in a wide range of catalytic reactions: isomerization of double C-C bonds [4,5], hydrogenation of multiple bonds [6][7][8], hydrogen-transfer reduction [9][10][11] and carbonylation [12][13][14][15].…”

Nanoscopic Metal Particles − Synthetic Methods and Potential Applications

“…Rhodium hydrosols, dissolved in water, were shown to be effective as hydrogenation catalysts in two‐phase systems, where the olefin formed the organic phase 185. Aqueous solutions of Moiseev’s giant Pd colloids [Figure 5, a)]73−78 were shown to catalyze a number of reactions in the “quasi‐homogeneous” phase, namely oxidative acetoxylation reactions,73 the oxidative carbonylation of phenol to diphenyl carbonate,186 the hydrogen‐transfer reduction of multiple bonds by formic acid,187 the reduction of nitriles and nitroarenes, and acetal formation,188 all with high turnover frequencies and significant lifetimes (see ref 11…”

Pd cluster catalysis: a review of reactions under anaerobic conditions

“…In fact, cluster 3 displayed high catalytic activity in the hydrogen-transfer reduction of various aromatic compounds (Table 3). 65 As seen in Table 3, nitrobenzene, nitrosobenzene and phenylhydroxylamine are readily reduced by HCOOH to form aniline in quantitative yields in solutions of cluster 3 (TOF B 3000 h~1 at 20 ¡C). The CxO and CxC bonds attached to the phenyl ring are hydrogenated in this catalytic system as readily as that of the N-containing functional groups in aromatic compounds.…”

“…In all of the experiments no alkylamines were formed until the nitrobenzene had been completely consumed. 65 These data suggest that under catalysis with Pd giant clusters, the redistribution of alkyl groups occurred, that is, a metathesis of amines.17 In order to check this suggestion, dimethylamine was maintained for 5 h in the MeCN solution containing cluster 3 and HCOOH. In contrast to the reduction of neat MeCN (see Table 2), only 10% of triethylamine and 5% of diethylamine were obtained, while dimethylethylamine composed 85% of the reaction products.…”