Solid-state characterisation of the[(eta~2-dppe)(eta~5-C5Me5)FeCO]~+ cation:an unexpected'oxidation'product of the[(eta~2-dppe)(eta~5-C5Me5)FeC indent to C(C6H4)NMe2]+radical cation

摘要

Several attempts to grow crystals of the[(eta~2-dppe)(eta~5-C5Me5)Fe-C indent to C-1,4-(C6H4)NMe2][PF6]radical cation(1~+PF_6~-)resulted in the isolation of crystals of the known iron(II)[(eta~2-dppe)(eta~5-C5Me5)FeCO][PF6]carbonyl adduct(2~+PF_6~-).We report here the solid-state structures of two polymorphs of this unexpected product,as well as the solid-state structure of a tetrafluoroborate analogue of 2~+for comparison purposes.Our investigations lead to a mechanistic proposal rationalising its formation from 1~+PF_6~-.In this respect,this work reveals one possible'decomposition'pathway undergone by electron-rich functional aryl-acetylide radical cations bearing electron-donating groups,when exposed to air.