Electro-organic reactions. Part 29: cathodic reduction activated by arene-chromium tricarbonyl complexation
Chromium tricarbonyl-arene complexes are easily reduced electrochemically with reduction potentials ca. 0.6V less than corresponding arenes; hence stilbene is activated towards hydrodimerisation and phenanthrene towards hydrogenation.
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Synthesis and properties of Fischer carbene complexes of N,N-dimethylaniline and anisole π-coordinated to chromium tricarbonyl
2018, Journal of Organometallic ChemistryCitation Excerpt :Thus, complexes {2-thienylC(OEt)W(CO)5} and {2-furylC(OEt)W(CO)5} oxidise at an anodic peak potential of 0.728 and 0.697 V, respectively, under similar conditions [41]. The irreversible reduction of the present complexes agrees with the known behaviour of other {η6-arene}Cr(CO)3 [53–55] derivatives (c. f. Epa = −1.59 V for {η6-OMeC6H5CO}Cr(CO)3, considering the 400 mV potential difference between the Ag/AgI and the Fc/Fc+ scales [56]), but also with that of Fischer type carbene complexes [16,57,58] (c. f. Epc = −1.564 V for {2-thienylC(OEt)W(CO)5} and −1.645 V for {2-furylC(OEt)W(CO)5}. While this makes an a priori assignment of the primary reduction site in the present complexes impossible, our quantum chemical calculations indicate that the LUMO of every complex is either biased towards the {arylC(OEt)W(CO)5} entity or delocalised over the entire molecule.
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