Abstract
The synthesis of the new mer or fac Fe(CO 2Me) 2(CO) 3 (L) (L=PMe 3: 2a; L=PPh 3: 2b; L=P(Cy) 3: 2c; L=P(OEt) 3: 2d) complexes of various electron densities has been realized in order to study the transesterification reactions between these methoxycarbonyl complexes and alcohols. The easy formation of [Fe(CO 2Me)(CO) 4(L)] [BF 4] by removing a methoxy group from these complexes clearly indicates that their methoxy group and particularly the one trans to the phosphane ligand are mobile. However whereas the unsubstituted complex Fe(CO 2Me) 2(CO) 4 ( 1) presents fast exchange reactions with ethanol, 2a and 2b are found unreactive towards the same reagent and 2d (L=P(OEt) 3) only undergoes slow transesterification reactions at 28°C. It is proposed an associative mechanism for this transesterification process probably induced by a preliminary nucleophilic addition of an alcohol molecule at a terminal carbonyl ligand prior to the elimination of the methoxy group of a methoxycarbonyl.
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