Insertion of Molecular Oxygen into a Palladium(II) Methyl Bond: A Radical Chain Mechanism Involving Palladium(III) Intermediates
作者： Luc Boisvert , Melanie C. Denney , Susan Kloek Hanson , Karen I. Goldberg
DOI: 10.1021/JA9061932
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摘要: The reaction of (bipy)PdMe2 (1) (bipy = 2,2′-bipyridine) with molecular oxygen results in the formation palladium(II) methylperoxide complex (bipy)PdMe(OOMe) (2). identity product 2 has been confirmed by independent synthesis. Results kinetic studies this unprecedented insertion into a palladium alkyl bond support involvement radical chain mechanism. Reproducible rates, attained presence initiator 2,2′-azobis(2-methylpropionitrile) (AIBN), reveal that is overall first-order (one-half-order both [1] and [AIBN], zero-order [O2]). unusual rate law (half-order [1]) implies proceeds mechanism differs significantly from those for organic autoxidations recently reported examples O2 Pd(II) hydride bonds. autoxidation 1 more closely related to found main group early transition metal comple...
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D. J. Carlsson, Keith U. Ingold, Kinetics and rate constants for the reduction of alkyl halides by organotin hydrides Journal of the American Chemical Society. ,vol. 90, pp. 7047- 7055 ,(1968) , 10.1021/JA01027A029
Debra Ann Ryan, James H. Espenson, Reaction of isopropyl(pentaaqua)chromium(III) ion with molecular oxygen in aqueous solution: kinetics of the chain reaction and effects of chain-breaking reagents and of variable ionic strength Journal of the American Chemical Society. ,vol. 104, pp. 704- 712 ,(1982) , 10.1021/JA00367A012
Michael M. Konnick, Shannon S. Stahl, Reaction of Molecular Oxygen with a PdII-Hydride To Produce a PdII-Hydroperoxide: Experimental Evidence for an HX-Reductive-Elimination Pathway Journal of the American Chemical Society. ,vol. 130, pp. 5753- 5762 ,(2008) , 10.1021/JA7112504
Gerardus M. Kapteijn, Athanasia Dervisi, Michel J. Verhoef, M.A. Frederik, H. van den Broek, David M. Grove, Gerard van Koten, Chemistry of diamino-ligated methylpalladium(II) alkoxides and aryloxides (Part II): methoxide formation and carbonylation reactions Journal of Organometallic Chemistry. ,vol. 517, pp. 123- 131 ,(1996) , 10.1016/0022-328X(96)06171-2
Frank R. Mayo, Free radical autoxidations of hydrocarbons Accounts of Chemical Research. ,vol. 1, pp. 193- 201 ,(1968) , 10.1021/AR50007A001
Irene Ara, Naima Chaouche, Juan Forniés, Consuelo Fortuño, Abdelaziz Kribii, Athanassios C. Tsipis, Formation of PPh2C6F5 through Phosphido Platinum and/or Palladium(III) Intermediates‖,⊥ Organometallics. ,vol. 25, pp. 1084- 1091 ,(2006) , 10.1021/OM0508029
David J. Cardin, Michael F. Lappert, Peter W. Lednor, Free-radical displacement reactions at a transition-metal centre: bimolecular homolytic substitution (S H2) at square-planar Pt II Journal of the Chemical Society, Chemical Communications. pp. 350- 350 ,(1973) , 10.1039/C39730000350
Alwyn G. Davies, K. U. Ingold, B. P. Roberts, R. Tudor, Homolytic organometallic reactions. Part II. The kinetics and rate constants for the autoxidation of organoboron compounds in solution Journal of The Chemical Society B: Physical Organic. pp. 698- 712 ,(1971) , 10.1039/J29710000698
Gregg A. Lane, William E. Geiger, Neil G. Connelly, Palladium(I) .pi.-radicals. Electrochemical preparation and study of their reaction pathways Journal of the American Chemical Society. ,vol. 109, pp. 402- 407 ,(1987) , 10.1021/JA00236A018
José Ruiz, M Teresa Martínez, Félix Florenciano, Venancio Rodríguez, Gregorio López, José Pérez, Penny A Chaloner, Peter B Hitchcock, None, Insertion Reactions into Pd−O and Pd−N Bonds: Preparation of Alkoxycarbonyl, Carbonato, Carbamato, Thiocarbamate, and Thioureide Complexes of Palladium(II) Inorganic Chemistry. ,vol. 42, pp. 3650- 3661 ,(2003) , 10.1021/IC0300058