High Pressure-derived Nonsymmetrical [CuO] Core for Room-temperature Methane Hydroxylation

Overview

Journal Sci Adv

Specialties Biology
Science

Date 2024 Oct 4

PMID 39365853

Authors

Peter E VanNatta

Cynthia M Archambault

Sicheng Wang

Tengteng Lyu

Jack DAmelio

Noah J Martell

Scott K Watson

Kunyu Wang

Zhenxian Liu

Matthew T Kieber-Emmons

Hao Yan

Affiliations

Soon will be listed here.

Abstract

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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