Promoting selective electrochemical CO reduction under unconventionally acidic conditions through secondary coordination sphere positioning.

While several studies have investigated the effects of protic secondary coordination sphere (SCS) groups on the kinetics of iron tetraphenylporphyrin (FeTPP) catalysed CO reduction, few have examined how a protic SCS might alter reaction selectivity. Under mildly acidic conditions, FeTPP-based catalysts are selective towards the 2e/2H reduction of CO to CO; however, in the presence of more acidic proton donors, indiscriminate proton transfers often result in parasitic H evolution. This report investigates how SCS amide positioning alters CO H selectivity during CO reduction with a series of four FeTPP isomers bearing SCS amides at varying positions around the porphyrin core: NH donors are placed at either the or position of the aryl porphyrin ring, as well as proximal (closer) or distal (farther away) to the porphyrin plane. In the presence of a conventional, weakly acidic proton source (phenol; p = 29.2 in MeCN), all isomers display the expected high faradaic efficiency (FE) towards CO (FE = 67-85%) along with minimal H evolution (FE = 3-13%). With a significantly stronger acid (3,5-bis(trifluoromethyl)phenol; p = 23.8 in MeCN), H becomes the major product when using the -distal or both isomers (FE = 45-65%) as well as unfunctionalized FeTPP (FE = 78%). Importantly, the -proximal isomer shows dramatically rescued CO selectivity under these unconventionally acidic conditions (FE = 83 ± 4%). These results show how proper SCS placement impacts reaction selectivity during CO reduction, particularly with respect to minimizing indiscriminate proton transfers that lead to undesirable reactivity.