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
|
|
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.