Giant Palladium Clusters as Catalysts of Oxidative Reactions of Olefins and Alcohols Full article
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Journal of Molecular Catalysis (Continued after 1994 as Journal of Molecular Catalysis A: Chemical and Journal of Molecular Catalysis B: Enzymatic)
ISSN: 0304-5102 |
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Output data | Year: 1989, Volume: 53, Number: 3, Pages: 315-348 Pages count : 34 DOI: 10.1016/0304-5102(89)80066-5 | ||||
Tags | Alcohols--Oxidation; Catalysis; Olefins--Oxidation | ||||
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Abstract:
Giant cationic palladium clusters approximated as Pd561L60(OAc)180 (L = phen, bipy) and Pd561phen60O60(PF6)60 were synthesized and characterized with high resolution TEM, SAXS, EXAFS, IR and magnetic susceptibility data. The results of these studies suggest that L and O ligands are bound to Pd atoms located on the surfaces of close-packed metal skeletons of the clusters, while OAc−1 and PF6− anions are outer-sphere ligands. Under mild conditions (293–363 K, l atm) the giant palladium clusters catalyze oxidative acetoxylation of ethylene into vinyl acetate, propylene into allyl acetate, and toluene into benzyl acetate; oxidation of primary aliphatic alcohols into esters; and conversion of aldehydes into acetals. Kinetics of oxidative acetoxylation of ethylene and propylene in solutions of the giant clusters were studied. A mechanism for these reactions is proposed, which includes the following steps: coordination of reagents by the cluster, oxidative addition of alkene to a Pd—Pd fragment and transfer of an electron pair from a Pd—H, Pd—vinyl, or Pd—allyl fragment to a coordinated molecule of oxidant (O2, peroxide, Pd(II)).
Cite:
Vargaftik M.N.
, Zagorodnikov V.P.
, Stolarov I.P.
, Moiseev I.I.
, Kochubey D.I.
, Likholobov V.A.
, Chuvilin A.L.
, Zamaraev K.I.
Giant Palladium Clusters as Catalysts of Oxidative Reactions of Olefins and Alcohols
Journal of Molecular Catalysis (Continued after 1994 as Journal of Molecular Catalysis A: Chemical and Journal of Molecular Catalysis B: Enzymatic). 1989. V.53. N3. P.315-348. DOI: 10.1016/0304-5102(89)80066-5 WOS Scopus РИНЦ
Giant Palladium Clusters as Catalysts of Oxidative Reactions of Olefins and Alcohols
Journal of Molecular Catalysis (Continued after 1994 as Journal of Molecular Catalysis A: Chemical and Journal of Molecular Catalysis B: Enzymatic). 1989. V.53. N3. P.315-348. DOI: 10.1016/0304-5102(89)80066-5 WOS Scopus РИНЦ
Dates:
Submitted: | Aug 10, 1988 |
Accepted: | Mar 6, 1989 |
Published print: | Aug 15, 1989 |
Published online: | Oct 2, 2001 |
Identifiers:
Web of science | WOS:A1989AQ00200010 |
Scopus | 2-s2.0-0024716992 |
Elibrary | 31074754 |
Chemical Abstracts | 1990:138372 |
Chemical Abstracts (print) | 112:138372 |
OpenAlex | W1979970534 |