Reactions of ditertiary phosphines with η6-arenetricarbonylmanganese cations
摘要:
Ditertiaryphosphines PPh2(CH2)nPPh2 (n = 1-3) react at room temperature with the eta-6-arenetricarbonylmanganese cations [(eta-6-XYC6H4)Mn(CO)3]+ (Ia, X = Y = H; Ib, X = Me, Y = H) by monocarbonyl substitution and formation of [(eta-6-XYC6H4)Mn(CO)2(eta-1-PPh2(CH2)nPPh2)]+. Prolonged refluxing results in metal-ring bond breaking and formation of cis- and trans-[Mn(CO)2(eta-2-PPh2CH2PPh2)2]+ and trans-[Mn(CO)2(eta-2-PPh2(CH2)2PPh2)2]+.Activation of a carbonyl group in [(eta-6-XYC6H4Mn(CO),(eta-1-PPh2(CH2)nPPh2)]+ by TMNO gives the series of chelate complexes [(eta-6-XYC6H4Mn(CO)(eta-2-PPh2(CH2)nPPh2)]+ (n = 1-3). The X-ray structure of the chelate with n = 3 is reported. In the case of [(eta-6-XYC6H4)Mn(CO)3]+ (Ic, X = Cl, Y = H); Id, X = Cl, Y = Me), formation of fac-Mn(CO)3(eta-2-PPh2(CH2)nPPh2)Cl (n = 1, 2) occurs, in a reaction analogous to that with monophosphines, see D.A. Brown, W.K. Glass and K.M. Kreddan, J. Organomet. Chem., 413 (1991) 233, but there was no evidence for ring adducts as intermediates.
Reactions of ditertiary phosphines with η6-arenetricarbonylmanganese cations
摘要:
Ditertiaryphosphines PPh2(CH2)nPPh2 (n = 1-3) react at room temperature with the eta-6-arenetricarbonylmanganese cations [(eta-6-XYC6H4)Mn(CO)3]+ (Ia, X = Y = H; Ib, X = Me, Y = H) by monocarbonyl substitution and formation of [(eta-6-XYC6H4)Mn(CO)2(eta-1-PPh2(CH2)nPPh2)]+. Prolonged refluxing results in metal-ring bond breaking and formation of cis- and trans-[Mn(CO)2(eta-2-PPh2CH2PPh2)2]+ and trans-[Mn(CO)2(eta-2-PPh2(CH2)2PPh2)2]+.Activation of a carbonyl group in [(eta-6-XYC6H4Mn(CO),(eta-1-PPh2(CH2)nPPh2)]+ by TMNO gives the series of chelate complexes [(eta-6-XYC6H4Mn(CO)(eta-2-PPh2(CH2)nPPh2)]+ (n = 1-3). The X-ray structure of the chelate with n = 3 is reported. In the case of [(eta-6-XYC6H4)Mn(CO)3]+ (Ic, X = Cl, Y = H); Id, X = Cl, Y = Me), formation of fac-Mn(CO)3(eta-2-PPh2(CH2)nPPh2)Cl (n = 1, 2) occurs, in a reaction analogous to that with monophosphines, see D.A. Brown, W.K. Glass and K.M. Kreddan, J. Organomet. Chem., 413 (1991) 233, but there was no evidence for ring adducts as intermediates.