Abstract
The structures of the diferrocenyl methyl cation (I) and protonated diferrocenyl ketone (II) are discussed in terms of modes of stabilisation. Evidence supporting the involvement of e 1 rather than e 2 orbitals in I is given with particular reference to values of Mössbauer quadrupole splittings ( QS) which are very much smaller than those of monoferrocenyl carbenium ions. The reaction of Fc 2CO and Fc 2CHOH with FeCl 3 was investigated using frozen solutions. For Fc 2CO, a redox reaction occurred resulting in the oxidation of only one iron site even with excess oxidant. These results were confirmed by cyclic voltammetry. For Fc 2CHOH, no redox reaction was observed but the FeCl 3 appears to coordinate to the alcoholic oxygen atom resulting in a marked diminution of QS. The observed QS values are rationalised in terms of electron donation by the ferrocenyl e 1 orbitals. This explanation is extended to cover previously reported Mössbauer spectra for biferrocenium and biferrocenylenium monocations.
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