High pressure–derived nonsymmetrical [Cu2O]2+ core for room-temperature methane hydroxylation

VanNatta, Peter E.; Archambault, Cynthia M.; Wang, Sicheng; Lyu, Tengteng; D’Amelio, Jack; Martell, Noah J.; Watson, Scott K.; Wang, Kunyu; Liu, Zhenxian; Kieber-Emmons, Matthew T.; Yan, Hao

doi:10.1126/sciadv.adq3366

Title: High pressure–derived nonsymmetrical [Cu₂O]²⁺ core for room-temperature methane hydroxylation

Journal Article · 03 October 2024 · Science Advances

DOI: https://doi.org/10.1126/sciadv.adq3366 · OSTI ID:2478821

^[1];

^[1]; Lyu, Tengteng ^[1]; D’Amelio, Jack ^[2];

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^[1];

^[4];

^[5]; Kieber-Emmons, Matthew T. ^[6];

^[1]

University of North Texas, Denton, TX (United States)
University of Illinois at Urbana-Champaign, IL (United States)
Iowa State University, Ames, IA (United States)
Texas A&M University, College Station, TX (United States)
University of Illinois, Chicago, IL (United States)
Cedar Crest College, Allentown, PA (United States)

Nonsymmetrical oxygen-bridged binuclear copper centers have been proposed and modeled as intermediates and transition states in several C–H oxidation pathways, leading to the postulation that structural dissymmetry enhances the reactivity of the bridging oxygen. However, experimentally characterizing the structure and reactivity of these transient species is remarkably challenging. Here, we report the high-pressure synthesis of a metastable nonsymmetrical dicopper-μ-oxo compound with exceptional reactivity toward the mono-oxygenation of aliphatic C–H bonds. The nonequivalent coordination environment of copper stabilizes localized mixed valency and greatly enhances the hydrogen atom abstraction activity of the bridging oxygen, enabling room-temperature hydroxylation of methane under pressure. These findings highlight the role of dissymmetry in the reactivity of binuclear copper centers and demonstrate precise control of molecular structures by mechanical means.

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Research Organization:: University of Illinois, Chicago, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE National Nuclear Security Administration (NNSA), Office of Defense Programs (DP); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: NA0003975; SC0012704

OSTI ID:: 2478821

Journal Information:: Science Advances, Journal Name: Science Advances Journal Issue: 40 Vol. 10; ISSN 2375-2548

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

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