SYNTHESIS OF (ETA(6)-C13H10)MN(CO)2LPF6 AND (ETA(6)-C13H9)MN(CO)2L COMPLEXES (L = PHOSPHINES AND PHOSPHITES) AND KINETIC-STUDIES OF ETA(6) TO ETA(5) RING SLIPPAGE REACTIONS

This report describes the syntheses and characterizations of (eta6-C13 H10)Mn(CO)2LPF6 and (eta6-C13H9)Mn(CO)2L complexes (L = P(OEt)3, PPh3, PEt3, and eta1-(diphos) (diphos = 1,2-bis(diphenylphosphino)ethane), and kinetic studies of (eta6-C13H9)Mn(CO)2L-->(eta5-C13H9)Mn(CO)2L rin g slippage reactions. DELTAH(double dagger) values for the eta6-->eta5 slippage reactions of the P(OEt)3 (26.4 kCal/mol), PPh3 (23.1 kcal mo l-1), and PEt3 (25.6 kcal mol-1) complexes are similar to values previ ously reported for CO and P(n-Bu)3 complexes. Tle unusually low value of DELTAH(double dagger) = 19.9 kcal/mol for the eta1-diphos complex i s attributed to an intermediate stabilized by an intramolecular nucleo philic attack of the free end of the diphos ligand on the metal center .