biostudies-literatureAdillon EHResnick Sustainability Institute for Science, Energy and Sustainability, California Institute of TechnologyBasic Energy SciencesNational Defense Science and Engineering Graduate30204-30211https://www.ebi.ac.uk/biostudies/studies/S-EPMC11544690biostudies-literatureUnknown146(44)Reagents capable of concerted proton-electron transfer (CPET) reactions can access reaction pathways with lower reaction barriers compared to stepwise pathways involving electron transfer (ET) and proton transfer (PT). To realize reductive multielectron/proton transformations involving CPET, one approach that has shown recent promise involves coupling a cobaltocene ET site with a protonated arylamine Brønsted acid PT site. This strategy colocalizes the electron/proton in a matter compatible with a CPET step and net reductive electrocatalysis. To probe the generality of such an approach a class of C,C'-diaryl-<i>o</i>-carboranes is herein explored as a conceptual substitute for the cobaltocene subunit, with an arylamine linkage still serving as a colocalized Brønsted base suitable for protonation. The featured <i>o</i>-carborane (Ph<b>Cb</b>Ph^N) can be reduced and protonated to generate an N-H bond with a weak effective bond dissociation free energy (BDFE_eff) of 31 kcal/mol, estimated with measured thermodynamic data. This N-H bond is among the lowest measured element-H bonds for analyzed nonmetal compounds. Distinct solid-state crystal structures of the one- and two-electron reduced forms of diaryl-<i>o</i>-carboranes are disclosed to gain insight into their well-behaved redox characteristics. The singly reduced, protonated form of the diaryl-<i>o</i>-carborane can mediate multi-ET/PT reductions of azoarenes, diphenylfumarate, and nitrotoluene. In contrast to the aforementioned cobaltocene system, available mechanistic data disclosed herein support these reactions occurring by a rate-limiting ET step and not a CPET step. A relevant hydrogen evolution reaction (HER) reaction was also studied, with data pointing to a PT/ET/PT mechanism, where the reduced carborane core is itself highly stable to protonation.Journal of the American Chemical SocietyA Carborane-Derived Proton-Coupled Electron Transfer Reagent.PMC11544690DE-SC0019136Peters JCAdillon EHfalseA Carborane-Derived Proton-Coupled Electron Transfer Reagent.Reagents capable of concerted proton-electron transfer (CPET) reactions can access reaction pathways with lower reaction barriers compared to stepwise pathways involving electron transfer (ET) and proton transfer (PT). To realize reductive multielectron/proton transformations involving CPET, one approach that has shown recent promise involves coupling a cobaltocene ET site with a protonated arylamine Brønsted acid PT site. This strategy colocalizes the electron/proton in a matter compatible with a CPET step and net reductive electrocatalysis. To probe the generality of such an approach a class of C,C'-diaryl-<i>o</i>-carboranes is herein explored as a conceptual substitute for the cobaltocene subunit, with an arylamine linkage still serving as a colocalized Brønsted base suitable for protonation. The featured <i>o</i>-carborane (Ph<b>Cb</b>Ph^N) can be reduced and protonated to generate an N-H bond with a weak effective bond dissociation free energy (BDFE_eff) of 31 kcal/mol, estimated with measured thermodynamic data. This N-H bond is among the lowest measured element-H bonds for analyzed nonmetal compounds. Distinct solid-state crystal structures of the one- and two-electron reduced forms of diaryl-<i>o</i>-carboranes are disclosed to gain insight into their well-behaved redox characteristics. The singly reduced, protonated form of the diaryl-<i>o</i>-carborane can mediate multi-ET/PT reductions of azoarenes, diphenylfumarate, and nitrotoluene. In contrast to the aforementioned cobaltocene system, available mechanistic data disclosed herein support these reactions occurring by a rate-limiting ET step and not a CPET step. A relevant hydrogen evolution reaction (HER) reaction was also studied, with data pointing to a PT/ET/PT mechanism, where the reduced carborane core is itself highly stable to protonation.2024-01-01T00:00:00Z2024 Nov2025-04-05T23:11:20.389Z2025-04-05T23:11:20.389ZS-EPMC115446903946681710.1021/jacs.4c09007