SYNTHESIS OF WATER-SOLUBLE, ALIPHATIC PHOSPHINES AND THEIR APPLICATION TO WELL-DEFINED RUTHENIUM OLEFIN METATHESIS CATALYSTS

Water-soluble aliphatic phosphines Cy(2)P(CH2)(2)N(CH3)(3)Cl-+(-) (14) , Cy(2)P[4-(N,N-dimethyl-piperidinium)]Cl-+(-) (15), Cy(2)P(CH2)(2)SO3 -Na+ (16), and CyP[(CH2)(2)N(CH3)(3)Cl-+(-)](2) (17) (Cy = cyclohexyl) were prepared from air-stable, borane-protected precursors. Spectrosc opic investigations of corresponding Pd(PR(3))(2)Cl-2 complexes were u sed to estimate the steric parameters of these new phosphines. Spectro scopic investigation of Ni(CO)(3)PR(3) complexes of the new phosphines indicated that phosphines bearing quaternary amine functionalities we re less electron donating than tricyclohexylphosphine, while the prese nce of a sulfonate group increased phosphine electron donation. Cation ic phosphines 14 and 15 were used to synthesize water-soluble rutheniu m carbene complexes of the type (Cy(2)PR)(2)Cl2Ru=CHPh. These complexe s initiate the ring-opening metathesis polymerization (ROMP) of functi onalized 7-oxanorbornenes in water, methanol, and aqueous emulsions.