Spectroelectrochemistry in the Monitoring of Chemical Reactions Following Electron Transfer

5 Spectroelectrochemistry in the Monitoring of Chemical Reactions Following Electron Transfer 

Compared to this plethora of redox-initiated reactions of carbon-rich complexes, the ones that have been studied by in situ techniques constitute a vanishing minority with not even a handful of examples in the literature. The most remarkable study deals with the shifting of the equilibrium between alkyne and vinylidene isomers by electron transfer.Thus, oxidation of the vinylidene complex [(ri -C6Me6)(CO)2Cr = C = C(SiMe3)2] generates a 

Shaw and coworkers have studied the anodically induced formation of the a,7i complex [ CpFe(CO)2 2(p-ri ri -C=CPh)] from Cp(CO)2Fe-C=CPh by infrared reflectance spectroelectrochemistry (IRRAS). This process goes along with the cleavage of the Fe-alkynyl bond and attack of the CpFe(CO)2 electrophile thus formed onto the parent alkynyl complex. Such processes are commonly dubbed as mother-daughter (or father-son) reactions. The identity of the electrogenerated product was established by comparing its IR absorbances to those of the independently prepared product. 

In our laboratories we have studied the reduction of r 2 -[Cl(dppm)2 Ru = C = C = CMePh] by voltammetric and in-situ techniques.The initially 

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