Thioethers cyclopentadienyliron cations

Polyaromatic Ethers and Thioethers Coordinated to Cyclopentadienyliron Cations... 

Cationic cyclopentadienyl iron fragments have been generated by photolysis of [(C5H5)Fe(C6H6)] [PF6] and shown to form transient cationic triple-decker sandwich complexes with [(t-Bu3C3P2)Fe(r-Bu2P3)]. Similar photolytic removal of cyclopentadienyliron moieties has been utilized as a key step in the synthesis of ether and thioether building blocks for polymer synthesis. ... 

Polyaromatic ethers coordinated to CpFe+ moieties have also been prepared via sequential S Ar reactions of chloroarene complexes with hydroquinone (189). The electrochemical behavior of cationic aromatic ether, thioether, and sul-fone complexes of cyclopentadienyliron has been studied using cyclic voltammetry and coulometry (190). Reaction of the aromatic ether complexes with sodium cyanide resulted in the formation of neutral adducts which imder-went oxidative demetallation to give the corresponding organic aromatic nitriles (191). 

The electrochemical properties of these cyclopentadienyliron-coordinated polyethers and ether-thioethers with norbomene units in their side chains were examined using cyclic voltammetry. Figure 24 shows the CV of polymer 48b at 0°C obtained with a sweep rate of 1 V/s in DMF. Reduction of the cationic 18-electron iron centers to the corresponding neutral 19-electron species occurred at 1/2=-1.08 V. 

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