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Propylene Oxidation by Palladium Nitro and Nitrato Complexes: In situ NMR and IR Studies Full article

Общее Language: Английский, Genre: Full article,
Status: Published, Source type: Original
Journal Journal of Organometallic Chemistry
ISSN: 0022-328X
Output data Year: 2004, Volume: 689, Number: 18, Pages: 2880-2887 Pages count : 8 DOI: 10.1016/j.jorganchem.2004.06.005
Tags Oxidation, Palladium nitro and nitrato complexes, Propylene
Authors Beck Irene E. 1 , Golovin Anatoli V. 1 , Likholobov Vladimir A. 1 , Gusevskaya Elena V. 2
Affiliations
1 Boreskov Institute of Catalysis, Novosibirsk, 630090, Russia
2 Departamento de Química-ICEx, Universidade Federal de Minas Gerais, 31270-901, Belo Horizonte, MG, Brésil

Funding (2)

1 Russian Foundation for Basic Research 96-15-97557
2 National Council for Scientific and Technological Development

Abstract: The mechanism of the propylene oxidation by Pd(NOn)Cl2 − m(CH3CN)2 complexes (n = 2, 3; m = 0, 1, 2) in chloroform solutions has been studied by 1H NMR and IR spectroscopy. The main reaction products are acetone and 2-nitropropylene, with their ratio depending on the equilibrium existing in the reaction solutions between palladium complexes containing NOn ligands bonded to a palladium atom via either an oxygen or a nitrogen atom. Reactivities of the oxygen bonded nitrato and nitrito complexes are significantly higher than that of the nitrogen bonded nitro complex. Various new organopalladium intermediates have been observed and monitored in situ. A reversible insertion of the coordinated propylene into the Pd–O or Pd–N bonds results in nitrato-, nitrito- and nitropalladation intermediates, which then decompose via a β-hydrogen elimination. Two isomers of the nitritopalladation intermediate have been detected, i.e., a palladium metallacycle and an open ring complex, with the latter being much more reactive towards the β-hydrogen elimination than the former. The decomposition of the nitrato- and nitritopalladation intermediates results in the organometallic precursor of acetone, i.e., an acetonylpalladium complex, and then in acetone itself. On the other hand, the nitropalladation intermediate originates 2-nitropropylene. In the presence of dioxygen, which re-oxidizes the nitrosyl groups, the acetone formation becomes a catalytic reaction with respect to both palladium and nitrogen.
Cite: Beck I.E. , Golovin A.V. , Likholobov V.A. , Gusevskaya E.V.
Propylene Oxidation by Palladium Nitro and Nitrato Complexes: In situ NMR and IR Studies
Journal of Organometallic Chemistry. 2004. V.689. N18. P.2880-2887. DOI: 10.1016/j.jorganchem.2004.06.005 publication_identifier_short.wos_identifier_type publication_identifier_short.scopus_identifier_type publication_identifier_short.rinz_identifier_type
Dates:
Submitted: Mar 23, 2004
Accepted: Jun 2, 2004
Published online: Jul 20, 2004
Published print: Sep 1, 2004
Identifiers:
publication_identifier.wos_identifier_type WOS:000223459700005
publication_identifier.scopus_identifier_type 2-s2.0-4344700394
publication_identifier.rinz_identifier_type 13451106
publication_identifier.accession_number_identifier_type 2004:626407
publication_identifier.chemical_accession_number_identifier_type 141:349712
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