Chapter 8: IR Spectro-electrochemistry and Group-6 α-diimine Catalysts of CO2 Reduction
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Published:21 May 2018
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Series: Energy and Environment Series
D. E. Ryan and F. Hartl, in Electrochemical Reduction of Carbon Dioxide: Overcoming the Limitations of Photosynthesis, ed. F. Marken and D. Fermin, The Royal Society of Chemistry, 2018, ch. 8, pp. 182-211.
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The complex [Re(CO)3(bpy)Cl] (bpy=2,2′-bipyridine) has been known for several decades as the catalyst precursor for both electrochemical and photochemical reduction of CO2, currently being outperformed by the cheaper and Earth-abundant manganese congeners. On the other hand, the catalytic potential of the related group-6 tetracarbonyl α-diimine complexes has only recently been discovered, showing particularly strong dependence on the cathodic material initially revealed by cyclic voltammetry and IR spectro-electrochemistry. This chapter tackles in some detail these general aspects, including fundamental experimental techniques used to investigate the cathodic behaviour and the electronic structures of group-6 [M(CO)4(α-diimine)] and related Re complexes as well as their reduced forms.