31P and 13C NMR studies on metal complexes of phosphorus-donors: Recognizing surprises

31P and 13C NMR methods are shown to provide the necessary clues to understand the unexpected and often very novel reactions of a series of ruthenium and palladium phosphine complexes based on the chiral biaryl-based phosphine auxiliaries BINAP, MeO-Biphep and MOP. Many of these reactions involve complexation of seemingly remote olefin moieties and subsequent P–C bond cleavage.