Oxygenation of cyclopalladated N,N-dimethylbenzylamine complexes by inorganic and organic peroxides: oxygen insertion into the palladium-carbon bond

Abstract

Oxygenation of cyclopalladated benzylamine\ncomplexes of the type [Pd(C&CH&Me2-2)X] ( I , X =\n(MeCN)*F4; 2, X = C&CH&Me2-2; 3, X = Oc&-\nCHflMez-2; 5, X = C1) with tert-butyl hydroperoxide\n(TBHP) and a vanadium catalyst (e.g. VO(acac)d affords\nthe corresponding phenolate complexes. The rate of\noxygenation increases strongly with the nucleophilicity\nof the organopalladium substrate. Complex dcrystallizes\nin the monoclinic space group P21/c with a = 11.171(1)\nA, b = 8.524(1) A, c = 18.101(1) A, /3 = 94.31(1)O, V =\n1718.7(3) A3, and Z = 4; the structure was refined to R\n= 0.026 and R, = 0.030 for 2938 observed reflections