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Volumn 593-594, Issue , 2000, Pages 211-225

The oxo-synthesis catalyzed by cationic palladium complexes, selectivity control by neutral ligand and anion

Author keywords

Aldehydes; Cationic palladium complexes; Copolymerization; Ketones; Oxo synthesis

Indexed keywords


EID: 0034649912     PISSN: 0022328X     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0022-328X(99)00554-9     Document Type: Article
Times cited : (79)

References (34)
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    • The term hydro-acylation has also been used to denote the reaction of olefins with aldehydes to produce ketones. Because of the analogy with hydroformylation, however, we prefer to reserve this term for the synthesis of ketones from olefins, carbon monoxide and hydrogen.
    • The term hydro-acylation has also been used to denote the reaction of olefins with aldehydes to produce ketones. Because of the analogy with hydroformylation, however, we prefer to reserve this term for the synthesis of ketones from olefins, carbon monoxide and hydrogen.
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    • An alternative possibility of intermediate Pd(IV)-dihydride species obtained via an oxidative pathway of Pd(II) and dihydrogen, similar to that proposed for hydrogenolysis of Ir(I)-acyl intermediates (P.P. Deutsch, R. Eisenberg, Organometallics 9 (1990) 709), is considered unlikely. The generation of Pd(IV) from Pd(II) species has, however, been demonstrated, but generally requires hard ligands and strong oxidants, such as alkyl iodides (see for example
    • An alternative possibility of intermediate Pd(IV)-dihydride species obtained via an oxidative pathway of Pd(II) and dihydrogen, similar to that proposed for hydrogenolysis of Ir(I)-acyl intermediates (P.P. Deutsch, R. Eisenberg, Organometallics 9 (1990) 709), is considered unlikely. The generation of Pd(IV) from Pd(II) species has, however, been demonstrated, but generally requires hard ligands and strong oxidants, such as alkyl iodides (see for example, P.K. Wong, J.K. Stille, J. Organomet. Chem. 70 (1974) 121).
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    • An alternative possibility of intermediate Pd(IV)-dihydride species obtained via an oxidative pathway of Pd(II) and dihydrogen, similar to that proposed for hydrogenolysis of Ir(I)-acyl intermediates (P.P. Deutsch, R. Eisenberg, Organometallics 9 (1990) 709), is considered unlikely. The generation of Pd(IV) from Pd(II) species has, however, been demonstrated, but generally requires hard ligands and strong oxidants, such as alkyl iodides (see for example, P.K. Wong, J.K. Stille, J. Organomet. Chem. 70 (1974) 121). (a) D. Milstein, J.K. Stille, J. Am. Chem Soc. 101 (1972) 4992.
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    • Strictly speaking, only one of the two CO insertions needs to be reversible. There is precedent for a difference in reversibility between n-acyl and iso-acyl formation in rhodium catalyzed hydroformylation (see
    • Strictly speaking, only one of the two CO insertions needs to be reversible. There is precedent for a difference in reversibility between n-acyl and iso-acyl formation in rhodium catalyzed hydroformylation (see R. Lazzaroni, P. Pertici, G.J. Fabrici, J. Mol. Catal. 58 (1990) 75).
    • (1990) J. Mol. Catal. , vol.58 , pp. 75
    • R. Lazzaroni1    P. Pertici2    G.J. Fabrici3
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    • Thesis, University of Amsterdam, The Netherlands
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