Insights into Amine Binding to Biaryl Phosphine Palladium Oxidative Addition Complexes and Reductive Elimination from Biaryl Phosphine Arylpalladium Amido Complexes via Density Functional Theory
| Autor: | Timothy E. Barder, Stephen L. Buchwald |
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| Rok vydání: | 2007 |
| Předmět: |
Models
Molecular Phosphines Surface Properties Molecular Conformation Crystallography X-Ray Biochemistry Medicinal chemistry Catalysis Reductive elimination chemistry.chemical_compound Colloid and Surface Chemistry XPhos Organic chemistry Amines Amination Biphenyl Compounds Amine binding General Chemistry Oxidative addition chemistry SPhos Thermodynamics Amine gas treating Oxidation-Reduction Palladium Phosphine |
| Zdroj: | Journal of the American Chemical Society. 129:12003-12010 |
| ISSN: | 1520-5126 0002-7863 |
| Popis: | We present results on the binding of a variety amines to monoligated oxidative addition complexes of the type L1Pd(Ar)Cl, where L is 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (SPhos, 1) or 2-dicyclohexylphosphino-2',4',6'-tri-ispropylbiphenyl (XPhos, 2). The binding of an amine to oxidative addition complexes composed of 1 and 2 is more complex than with smaller ligands as intermediate Pd(II) complexes with bulky biaryl phosphine ligands disfavor amine binding to favorable conformations of oxidative addition complexes. Additionally, thermodynamic and kinetic parameters for reductive elimination from complexes of the type L1Pd(amido)Ph (where amido = EtNH, Me2N, PhNH) are discussed. From this data, we suggest a possible mechanism for (biaryl phosphine) Pd-catalyzed amination reactions that is more intricate than previously thought. |
| Databáze: | OpenAIRE |
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