Matches in SemOpenAlex for { <https://semopenalex.org/work/W3206741779> ?p ?o ?g. }
Showing items 1 to 80 of
80
with 100 items per page.
- W3206741779 abstract "The selective 4e–/4H+ reduction of dioxygen to water is an important reaction that takes place at the cathode of fuel cells. Monomeric aromatic tetrapyrroles (such as porphyrins, phthalocyanines, and corroles) coordinated to Co(II) have been considered as oxygen reduction catalysts due to their low cost and relative ease of synthesis. How- ever, these systems have been repeatedly shown to be selective for O2 reduction by the less desired 2e –/2H+ pathway to yield hydrogen peroxide. Herein, we report the initial synthesis and study of a Co(II) tetrapyrrole complex based upon a non-aromatic isocorrole scaffold that is competent for 4e–/4H+ ORR. This Co(II) 10,10-dimethyl isocorrole (Co[10- DMIC]) is obtained in a just four simple steps and excellent yield from a known dipyrromethane synthon. Evaluation of the steady state spectroscopic and redox properties of Co[10-DMIC] against those of Co(II) porphyrin ([Co(TPFPP)]) and corrole ([Co(TPFPC)(PPh3)]) homologs demonstrated that the light harvesting and electrochemical properties of the isocorrole are distinct from those displayed by more traditional aromatic tetrapyrroles. Further, investigation of the ORR activity of Co[10-DMIC] using a combination of electrochemical and chemical reduction studies revealed that this simple, unadorned monomeric Co(II) tetrapyrrole is ~85% selective for the 4e–/4H+ reduction of O2 to H2O over the more kinetically facile 2e–/2H+ process that delivers H2O2. By contrast, the same ORR evaluations conducted for the Co(II) porphyrin and corrole homologs demonstrated that these traditional aromatic systems catalyze the 2e–/2H+ conversion of O2 to H2O2 with near complete selectivity. Despite being a simple, easily prepared, monomeric tetrapyrrole platform, Co[10-DMIC] supports an ORR catalysis that has historically only been achieved using elaborate porphyrinoid-based architectures that incorporate pendant proton-transfer groups, ditopic molecular clefts, or which impose cofacially ori- ented O2 binding sites. Accordingly, Co[10-DMIC] represents the first simple, unadorned, monomeric metalloisocorrole complex that can be easily prepared and which shows a privileged performance for the 4e–/4H+ peractivation of O2 to water as compared to other simple Co(II) tetrapyrroles." @default.
- W3206741779 created "2021-10-25" @default.
- W3206741779 creator A5013225612 @default.
- W3206741779 creator A5031648869 @default.
- W3206741779 creator A5034430874 @default.
- W3206741779 creator A5043489735 @default.
- W3206741779 creator A5054180573 @default.
- W3206741779 creator A5073112786 @default.
- W3206741779 date "2021-10-07" @default.
- W3206741779 modified "2023-10-15" @default.
- W3206741779 title "An Easily Prepared Monomeric Cobalt(II) Tetrapyrrole Complex that Efficiently Promotes the 4e–/4H+ Peractivation of O2 to Water" @default.
- W3206741779 doi "https://doi.org/10.33774/chemrxiv-2021-vjzll" @default.
- W3206741779 hasPublicationYear "2021" @default.
- W3206741779 type Work @default.
- W3206741779 sameAs 3206741779 @default.
- W3206741779 citedByCount "0" @default.
- W3206741779 crossrefType "posted-content" @default.
- W3206741779 hasAuthorship W3206741779A5013225612 @default.
- W3206741779 hasAuthorship W3206741779A5031648869 @default.
- W3206741779 hasAuthorship W3206741779A5034430874 @default.
- W3206741779 hasAuthorship W3206741779A5043489735 @default.
- W3206741779 hasAuthorship W3206741779A5054180573 @default.
- W3206741779 hasAuthorship W3206741779A5073112786 @default.
- W3206741779 hasBestOaLocation W32067417791 @default.
- W3206741779 hasConcept C134121241 @default.
- W3206741779 hasConcept C147789679 @default.
- W3206741779 hasConcept C166940927 @default.
- W3206741779 hasConcept C17525397 @default.
- W3206741779 hasConcept C178790620 @default.
- W3206741779 hasConcept C179104552 @default.
- W3206741779 hasConcept C181199279 @default.
- W3206741779 hasConcept C185592680 @default.
- W3206741779 hasConcept C191897082 @default.
- W3206741779 hasConcept C192562407 @default.
- W3206741779 hasConcept C21951064 @default.
- W3206741779 hasConcept C2777710969 @default.
- W3206741779 hasConcept C2778495548 @default.
- W3206741779 hasConcept C2779480358 @default.
- W3206741779 hasConcept C515602321 @default.
- W3206741779 hasConcept C521977710 @default.
- W3206741779 hasConcept C52859227 @default.
- W3206741779 hasConcept C55904794 @default.
- W3206741779 hasConcept C75473681 @default.
- W3206741779 hasConceptScore W3206741779C134121241 @default.
- W3206741779 hasConceptScore W3206741779C147789679 @default.
- W3206741779 hasConceptScore W3206741779C166940927 @default.
- W3206741779 hasConceptScore W3206741779C17525397 @default.
- W3206741779 hasConceptScore W3206741779C178790620 @default.
- W3206741779 hasConceptScore W3206741779C179104552 @default.
- W3206741779 hasConceptScore W3206741779C181199279 @default.
- W3206741779 hasConceptScore W3206741779C185592680 @default.
- W3206741779 hasConceptScore W3206741779C191897082 @default.
- W3206741779 hasConceptScore W3206741779C192562407 @default.
- W3206741779 hasConceptScore W3206741779C21951064 @default.
- W3206741779 hasConceptScore W3206741779C2777710969 @default.
- W3206741779 hasConceptScore W3206741779C2778495548 @default.
- W3206741779 hasConceptScore W3206741779C2779480358 @default.
- W3206741779 hasConceptScore W3206741779C515602321 @default.
- W3206741779 hasConceptScore W3206741779C521977710 @default.
- W3206741779 hasConceptScore W3206741779C52859227 @default.
- W3206741779 hasConceptScore W3206741779C55904794 @default.
- W3206741779 hasConceptScore W3206741779C75473681 @default.
- W3206741779 hasLocation W32067417791 @default.
- W3206741779 hasLocation W32067417792 @default.
- W3206741779 hasOpenAccess W3206741779 @default.
- W3206741779 hasPrimaryLocation W32067417791 @default.
- W3206741779 hasRelatedWork W2003808278 @default.
- W3206741779 hasRelatedWork W2083277986 @default.
- W3206741779 hasRelatedWork W2095739344 @default.
- W3206741779 hasRelatedWork W2127468324 @default.
- W3206741779 hasRelatedWork W2323145757 @default.
- W3206741779 hasRelatedWork W2889096781 @default.
- W3206741779 hasRelatedWork W3203537173 @default.
- W3206741779 hasRelatedWork W4211024931 @default.
- W3206741779 hasRelatedWork W4254095052 @default.
- W3206741779 hasRelatedWork W4321330999 @default.
- W3206741779 isParatext "false" @default.
- W3206741779 isRetracted "false" @default.
- W3206741779 magId "3206741779" @default.
- W3206741779 workType "article" @default.