Abstract
The difference in reactivity towards RhI between simple tertiary phosphines and diphenylphosphino-acetic acid can be explained by the assumption that the latter ligand, besides monodentate P bonding, tends also to react by oxidative addition of its carboxyl group, yielding P,O-chelated rhodium(III) complexes. Crystal structures of the final product, fac-[Rh(Ph2PCH2CO2)3]·PhNO2·H2O, and of the key intermediate, mer-[RhCl(H)(Ph2PCH2CO2)(Ph2PCH2CO2H)2]·C4H8O, were determined. The latter structure is unique in that it contains both hydride and a carboxylic proton in one molecule.
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