Density functional theory study of palladium-catalyzed aryl-nitrogen and aryl-oxygen bond formation

A density functional theory study of the kinetics and thermodynamics of Pd-phosphine-catalyzed heteroatom bond formation ArX + REHn ->[PD]ArE(H)(n-1)R + HX was carried out. Individual steps in the catalytic cycle-ArX oxidative addition, REHn coordination, HX loss and ArE(H)(n-1)R reductive elimination and beta-hydride elimination-were investigated. The effects of modification of the ligand (PH3 versus PMe3) leaving group (X = Cl versus X = Br), heteroatom substrate (REHn = H2O and NH3), aryl (Ar = phenyl, p-cyanophenyl, p-aminophenyl, pyridyl) and metal coordination number (Pd(PH3) versus Pd(PH3)(2)) were investigated. Copyright (c) 2004 John Wiley & Sons, Ltd.