74563-04-5Relevant academic research and scientific papers
Unusual case of catalysis by palladium clusters
Stolarov,Dobrokhotova,Kryukova,Kozitsyna,Gekhman,Vargaftik,Moiseev
, p. 803 - 806 (2007/10/03)
An unusual for Pd catalysts dehydration of α-alkyl and α, α′-dialkylbenzyl alcohols PhCR′R″OH (R′ = H, Me, Et, Bu; R″ = H, Me) occurs in the presence of the palladium(I) cluster [Pd4(CO)4(OAc)4] (1) in an inert atmosphere to form ethers PhCR′R″-O-CR′ R″ and water. The catalyst is an intermediate of cluster 1 reduction to Pd black, while neither the starting cluster 1, nor Pd black, which is the decomposition product, are active in the catalysis of this reaction.
Reactivity of bismuth(III) halides towards alcohols. A tentative to mechanistic investigation
Keramane, El Mehdi,Boyer, Bernard,Roque, Jean-Pierre
, p. 1909 - 1916 (2007/10/03)
The reactivity of bismuth(III) halides (BiX3; X=Cl, Br and I) towards a series of alcohols has been investigated. Three different reactions have been studied, namely: halogenation, dehydration and etherification. The behaviour of these bismuth derivatives was found to depend on the nature of the halide bonded to the bismuth atom. Their reactivities can be interpreted on the basis of the Hard and Soft Acids and Bases (HSAB) principle. A mechanism is proposed which involves the formation of a complex of the alcohol with Bi(III).
Transformation of Carbinols by RuCl2(PPh3)3 and by Some Other Transition-Metal Catalysts
Pri-Bar, Ilan,Buchman, Ouri,Schumann, Hebert,Kroth, Heinz J.,Blum, Jochanan
, p. 4418 - 4428 (2007/10/02)
Several platinoid metal catalysts have been shown to promote reductive coupling, dehydration, disproportionation, and dehydrogenation of diarylcarbinols.Mechanistic studies were performed at 180-210 deg C with benzhydrol as substrate and RuCl2(PPh3)3 as catalyst.In aromatic hydrocarbon solvents the main process is reductive coupling.In this medium solvated RuCl2(PPh3)2 is suggested to be the active catalyst.In dimethyl sulfoxide the starting complex is transformed initially into RuCl2(PPh3)(Me2SO)2 and causes chiefly carbinol dehydrogenation.Ruthenium alkoxides are implied as common reaction intermediates in all four catalyses.Ruthenium hydrides are suggested to take part in the reductive coupling, disproportionation, and dehydrogenation processes.Some aliphatic and primary aromatic alcohols that do not react by themselves in the presence of RuCl2(PPh3)3 can both serve as active hydrogen donors and form crossover products in the presence of secondary and tertiary aromatic carbinols.
