The variable-temperature 'H and 13C NMR studies of a series of isomeric "flyover bridge" complexes M2(CO)gL(m-[C(R)=C(R')]2(MC0 )= Ru, Fe; L = CO, PPh,, AsPh3, SbPh,; R, R' = Me, Ph) show that a fluxional process of the dienone ligand, leading to the exchange of s- and p-bonds at the two metal centers is occurring in these compounds on the NMR time scale. The activation energy for this process in the entire series is essentially invariant (AG* = (70-76) f 5 kJ/mol) with the nature of M and L and is apparently independent of localized carbonyl exchange at each M(CO), unit.
Dynamic Behaviour of the Flyover Bridge Complexes M2(CO)5L [m- (C(R)=C(R'))2CO]( M=Ru, Fe; L=CO, PPh3, AsPh3, SbPh3; R.R'=Me, Ph )
AIME, Silvio;GOBETTO, Roberto;OSELLA, Domenico;MILONE, Luciano;
1986-01-01
Abstract
The variable-temperature 'H and 13C NMR studies of a series of isomeric "flyover bridge" complexes M2(CO)gL(m-[C(R)=C(R')]2(MC0 )= Ru, Fe; L = CO, PPh,, AsPh3, SbPh,; R, R' = Me, Ph) show that a fluxional process of the dienone ligand, leading to the exchange of s- and p-bonds at the two metal centers is occurring in these compounds on the NMR time scale. The activation energy for this process in the entire series is essentially invariant (AG* = (70-76) f 5 kJ/mol) with the nature of M and L and is apparently independent of localized carbonyl exchange at each M(CO), unit.
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