Synthesis, Characterization, and Reactivity of [((iPr)2P(CH2)3P(iPr)2)(PCy3)PdH][OR]

The preparation of (DIPPP)Pd(PR3) and [(DIPPP)(PR3)PdH][OR‘] (DIPPP = bis(1,3-diisopropylphosphino)propane; R = Cy, Et; R‘ = Ar, CF3SO2) is reported. (DIPPP)Pd(PCy3) and [(DIPPP)(PCy3)PdH][CF3SO3] have been structurally characterized. (DIPPP)Pd(PR3) complexes catalyze the reaction of ethylene with carbon monoxide and phenols to give aryl propionates. In situ 31P NMR experiments have shown that the resting state of the catalyst in these transformations is the binuclear species [{(DIPPP)Pd}2(μ-H)(μ-CO)][OPh].