Synthesis, Kinetics, and Stereochemistry of P-C Bond Breaking and P-C Bond Making Reactions: Ruthenium-Arene Binap Chemistry

The syntheses of a set of new arene Ru complexes containing the ligand P(OH)(OR)Ph are reported. Kinetic results for the rapid stereospecific alcoholysis of a Ru-{P(OH)Ph2} moiety with ROH to give a phenyl RuP(OH)(OR)Ph fragment are given. The protonation chemistry of this new Ru-phenyl {P(OH)(OR)Ph} species, using an excess of triflic acid in CD2Cl2, affords a reaction in which the Ru-phenyl group migrates from the metal back to the P atom without loss of stereogenicity at the Ru atom. The ease and stereospecificity of these reactions are rationalized.