To celebrate the 15th anniversary of Chemical Science, we invited authors who published with the journal in its early years and contributed seminal papers since then to revisit their original work and reflect on how their field has evolved. In their new Reflection article, Alicia Casitas and Xavi Ribas return to their influential 2013 review on high‑valent copper species to examine a decade of discovery, debate, and conceptual refinement in organometallic copper(III) chemistry.
Read the Reflection, for free, here: https://doi.org/10.1039/D5SC90259B

In 2013 the notion of isolable organocopper(III) complexes was still taking shape. The field was energized by the finding of copper‑catalysed C–H and C–X bond‑forming reactions, yet there remained fundamental questions:
How do these reactive species behave? What governs their selectivity? And what does “Cu(III)” truly mean in systems where ligand effects blur formal oxidation states?
Casitas and Ribas chart how these questions have guided the evolution of the field, highlighting both mechanistic breakthroughs and the nuanced electronic structures that continue to challenge understanding to this day.
Dissecting a Promiscuous Catalyst
Across different ligand environments and substrates, organocopper(III) complexes exhibit dramatically varied mechanistic profiles. These species sometimes follow pathways reminiscent of classical organometallic reductive elimination, other times behaving showcasing radical or redox activity. This mechanistic “promiscuity” has pushed chemists to refine both computational tools and spectroscopic strategies to capture transient structures.
Recent research published in Chemical Science illustrates these complexities. Fan and co‑workers exploited the distinct hydrogen‑atom‑transfer (HAT) and radical‑capture reactivity of two different copper(III) complexes, Cu(III)-OH and Cu(III)-F, to develop a decoupled approach to C(sp³)-H fluorination (https://doi.org/10.1039/D5SC06381G). This strategy sidesteps the longstanding challenge of expecting a single high‑valent metal complex to excel at both HAT and radical capture.

Illuminating Radical Pathways
The Reflection also highlights the continuing debate over the nature of formal Cu(III), particularly in CF₃‑bearing complexes. Photochemical activation strategies have provided a powerful platform for interrogating these species. In an elegant demonstration, Motornov, Beier and co‑workers used violet‑light irradiation to sequentially release all four CF₃ groups from a tetrakis(trifluoromethyl)cuprate(III) complex, enabling efficient C-H trifluoromethylation of (hetero)arenes and even biomolecules (https://doi.org/10.1039/D5SC07405C). Their mechanistic studies reinforce how photochemistry can reveal hidden facets of high‑valent copper intermediates while affording practical transformations.
The interplay of radical and organometallic pathways also features in the combined computational and experimental work of Mandal, Stahl and colleagues (https://doi.org/10.1039/D3SC03597B). Their study dissects N-fluorobenzenesulfonimide (NFSI)-based radical-relay reactions, mapping selectivity trends and evaluating competing pathways such as radical–polar crossover and reductive elimination from formal Cu(III) species.

Expanding the Copper Redox Landscape
New insights into copper(I)/copper(III) redox cycles continue to appear in unexpected places. Sneddon, Kerr and collaborators conducted a deep mechanistic study of a copper(I)-catalysed sulfonylative Suzuki–Miyaura reaction (https://doi.org/10.1039/D3SC01337E), revealing not only the expected Cu(I)/Cu(III) pathways but also a competing Cu(II)-mediated route. Their work highlights the interconnectedness of copper’s redox chemistry, which is explored in the Reflection article from Casitas and Ribas.
Following their early contribution to Chemical Science, this Reflection captures not just how far copper(III) chemistry has come, but how vibrant, and mechanistically rich, future research may be.

































