Carbon–oxygen and carbon–hydrogen bond cleavage in the reaction of [{Ru(CO)25-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.

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