Charge-Transfer Coordination to Metallocomplex Ion-Radicals

This problem will be considered on the basis of charge-transfer coordination of organic polynitriles to substituted ferrocenes. The practical significance of the charge-transfer coordinative species (salts) is their ferromagnetic behavior (see Section 8.5). The salts contain the cation-radical and anion-radical counterparts. Peculiarities in electronic structures of the cation-radical parts within the salts are topics of our interest. 

It should be pointed out that the treatment of phosphorus or sulfur donors bearing ferrocenyl groups with diiodine results in the formation of molecular charge-transfer adducts without simultaneous oxidation of the ferrocenyl groups (Durfey et al. 2000, Gridunova et al. 1982). At the same time, the reaction of 4-ferrocenyl-l,3-dithiolene-2-thione with diiodine leads to a charge-transfer complex in which the iron has been oxidized from Fe to Fe . This was confirmed by magnetic measurements and Moessbauer spectroscopy (Allen et al. 2003). 

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