biostudies-literatureUnknownQueener JAHigh-valent metal intermediates play a key role in C(sp³)-H functionalization reactions in both enzymatic catalysis and organometallic chemistry. Despite its generality, this strategy often requires a single metal complex to efficiently mediate both hydrogen atom transfer and radical capture-a combination challenging to achieve. To overcome this limitation, we propose a decoupled approach, where separate high-valent metal complexes independently perform hydrogen atom transfer (HAT) and radical capture (RC). As a proof of concept, we leveraged the complementary reactivity of copper(iii) hydroxide (efficient for HAT) and copper(iii) fluoride (efficient for RC) to develop a decoupled ¹⁸F-fluorination protocol. The distinct reactivity of copper(iii) hydroxide and copper(iChemical sciencehttps://www.ebi.ac.uk/biostudies/studies/S-EPMC12606465biostudies-literatureDistinct hydrogen atom transfer and radical capture reactivity of copper(iii) OH/F complexes enables site-selective C(sp<sup>3</sup>)-H <sup>18</sup>F-fluorination.PMC12606465Tang JAsor AFan JQueener JABall MAPZhang SfalseDistinct hydrogen atom transfer and radical capture reactivity of copper(iii) OH/F complexes enables site-selective C(sp<sup>3</sup>)-H <sup>18</sup>F-fluorination.High-valent metal intermediates play a key role in C(sp³)-H functionalization reactions in both enzymatic catalysis and organometallic chemistry. Despite its generality, this strategy often requires a single metal complex to efficiently mediate both hydrogen atom transfer and radical capture-a combination challenging to achieve. To overcome this limitation, we propose a decoupled approach, where separate high-valent metal complexes independently perform hydrogen atom transfer (HAT) and radical capture (RC). As a proof of concept, we leveraged the complementary reactivity of copper(iii) hydroxide (efficient for HAT) and copper(iii) fluoride (efficient for RC) to develop a decoupled ¹⁸F-fluorination protocol. The distinct reactivity of copper(iii) hydroxide and copper(i2025-01-01T00:00:00Z2025 Nov2026-06-05T13:45:14.112Z2026-05-17T03:13:33.405ZS-EPMC126064654123507210.1039/d5sc06381g