Electrocatalyst decomposition pathways: torsional strain in a second sphere proton relay shuts off CO₂RR in a Re(2,2′-bipyridyl)(CO)₃X type electrocatalyst

Abstract

Group 7 tris(carbonyl) bipyridine complexes have been well explored as important CO2 reduction reaction (CO2RR) electrocatalysts and now represent an excellent platform for catalyst design. Recent synthetic focus has been...

Kinetic Isotope Effects and the Mechanism of CO2 Insertion into the Metal-Hydride Bond of fac-(bpy)Re(CO)3H

“…Development of octahedral rhenium and manganese complexes or precursors related to 1 –Re–H continue to be of great current interest for use as catalysts, electrocatalysts, and photocatalysts for various transformations of CO 2 . − Thus, knowledge of the mechanism of the CO 2 insertion step in this system is of fundamental interest and is vital when the calculations are invoked to interpret experimental results or to design new catalysts for CO 2 transformations. Yet while gas-phase calculations found TS2 to mediate “smooth” CO 2 insertion in 1 –Re–H, more recent studies in DMF and MeCN solvent continuums reported only TS1 . , Likewise, while calculations on CO 2 insertion in the manganese complex 2 –Mn–H in Scheme invoked a role for TS2 , a more recent study on a closely related complex calculated only TS1 …”

1,2-Azolylamidino ruthenium(ii) complexes with DMSO ligands: electro- and photocatalysts for CO2 reduction

“…The latter have been taken into consideration only very recently, when the first reports on the role of pendant groups that may lead to supramolecular arrangements have been described. 8 However, synthetic methods for substituted bipy ligands are usually difficult and/or tiresome, and thus the alternative of coupling two monodentate ligands to afford a chelating diimine ligand appears as a straightforward method in order to obtain N,N-chelating ligands by accessible synthetic paths. 9 1,2-Azolylamidino ligands fulfill these requirements, as they can be easily obtained in situ by the coupling reaction of 1,2-azoles and coordinated nitriles (Scheme 1).…”