Carbon–oxygen and carbon–hydrogen bond cleavage in the reaction of [{Ru(CO)2(η5-C5H)5}2]+ with phosphite and phosphine ligands

Abstract

Reaction of [{Ru(CO)₂(cp)}₂](cp =η⁵-cyclopentadienyl) with P(OR)₃ ligands (R = Me, Et, or Buⁿ) yields [Ru(CO)₂(cp)R], [Ru(cp){P(OR)₃}₂{P(O)(OR)₂}], and [Ru(CO)(cp){P(OR)₃}{P(O)(OR)₂}] complexes resulting from C–O bond cleavage. The former complexes were characterized by reaction with PPh₃ which yields the acyl [Ru(CO)(cp)(COR)(PPh₃)] derivative. Reaction of [{Ru(CO)₂(cp)}₂] with PPr₃ and PMe₂Ph proceeds to yield a mixture of the substituted dimer [Ru₂(CO)₃(cp)₂(PR₃)] and the hydrides [Ru(CO)_x(cp)H(PR₃)_2–x](x= 0 or 1) depending on the reaction conditions. The mechanisms of these reactions and the fluxionality of the substituted dimers are discussed.