MECHANISTIC STUDIES ON THE IRON-PROMOTED DEAMINATION REACTIONS OF 7-AZANORBORNADIENE DERIVATIVES

The reaction mechanism for the fragmentation of 7-azanorbornadiene der ivatives (ANB; 7-azabicyclo[2.2.1]hepta-2,5-diene) mediated by iron ca rbonyl compounds was analyzed by substituent effects. The reactions pr oceed through two stages: a tetracarbonyliron complex (ANB)Fe(CO)(4) f orms first followed by a tricarbonyliron complex (ANB)Fe(CO)(3). A lin ear free energy correlation was found for the decomposition of the lat ter group of complexes, which implied the existence of a polar transit ion state. The proposed mechanism was then confirmed by the isolation of new products from certain 2-tosyl ANB complexes in a related reacti on.