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Phosphorus-Ligand Redox Cooperative Catalysis: Unraveling Four-Electron Dioxygen Reduction Pathways and Reactive Intermediates.
Kim, Sung Gyu; Kim, Dongyoung; Oh, Jinrok; Son, Yeong Jun; Jeong, Sangmin; Kim, Joonghan; Hwang, Seung Jun.
Afiliación
  • Kim SG; Department of Chemistry, Pohang University of Science and Technology, Pohang 37673, Republic of Korea.
  • Kim D; Department of Chemistry, Pohang University of Science and Technology, Pohang 37673, Republic of Korea.
  • Oh J; Department of Chemistry, Pohang University of Science and Technology, Pohang 37673, Republic of Korea.
  • Son YJ; Department of Chemistry, Pohang University of Science and Technology, Pohang 37673, Republic of Korea.
  • Jeong S; Department of Chemistry, Pohang University of Science and Technology, Pohang 37673, Republic of Korea.
  • Kim J; Department of Chemistry, The Catholic University of Korea, Bucheon 14662, Republic of Korea.
  • Hwang SJ; Department of Chemistry, Pohang University of Science and Technology, Pohang 37673, Republic of Korea.
J Am Chem Soc ; 2024 Apr 10.
Article en En | MEDLINE | ID: mdl-38597246
ABSTRACT
The reduction of dioxygen to water is crucial in biology and energy technologies, but it is challenging due to the inertness of triplet oxygen and complex mechanisms. Nature leverages high-spin transition metal complexes for this, whereas main-group compounds with their singlet state and limited redox capabilities exhibit subdued reactivity. We present a novel phosphorus complex capable of four-electron dioxygen reduction, facilitated by unique phosphorus-ligand redox cooperativity. Spectroscopic and computational investigations attribute this cooperative reactivity to the unique electronic structure arising from the geometry of the phosphorus complex bestowed by the ligand. Mechanistic study via spectroscopic and kinetic experiments revealed the involvement of elusive phosphorus intermediates resembling those in metalloenzymes. Our result highlights the multielectron reactivity of phosphorus compound emerging from a carefully designed ligand platform with redox cooperativity. We anticipate that the work described expands the strategies in developing main-group catalytic reactions, especially in small molecule fixations demanding multielectron redox processes.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Am Chem Soc Año: 2024 Tipo del documento: Article Pais de publicación: Estados Unidos
Texto completo
Añadir a Mi BVS
Imprimir
XML
PubMed Links
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Am Chem Soc Año: 2024 Tipo del documento: Article Pais de publicación: Estados Unidos