Correction to “First Row Transition Metals in Olefin Metathesis: The Role of Iron and Manganese”

A. Brotons Rufes, J. P. Martínez, N. Joly, S. Gaillard, J.-L. Renaud, S. Posada Pérez, A. Poater, ChemCatChem 2025, 17, e00570.

https://doi.org/10.1002/cctc.202500570

After publication, it was brought to our attention that the discussion of the article by Lincoln and Iluc, cited as Ref. [92] in our work, was lacking. The supplemented discussion follows:

The article by Lincoln and Iluc^[92] reports the metathesis of olefins catalyzed by iron carbene complexes. Here, the authors demonstrate that a pincer-ligated iron complex can form a metallacyclobutane intermediate upon reaction with norbornadiene and its derivatives, validating a key intermediate previously elusive for first-row metal-catalyzed olefin metathesis.

This study highlights the unique ability of a PC(sp²)P iron complex to activate a strained olefin through a [2 + 2] addition to form a well-characterized metallacyclobutane intermediate, which subsequently converts to a ring-opened iron alkylidene. Importantly, the formation and breakdown of this intermediate obeys the classical Chauvin olefin metathesis mechanism, a process previously predominantly associated with late transition metal species.

The authors provide extensive structural, spectral, and magnetic data to characterize the intermediate, adding credibility to their proposal. The crystallographically defined structures of the metallacyclobutane and its ring-opened counterpart illuminate key bond formations and cleavages that underpin the metathesis process. Furthermore, the observation of a reversible formation of the ring-opened intermediate upon addition of phosphine underscores a delicate thermodynamics that controls this transformation, reflecting the fundamental role of phosphine dissociation in accessing reactive species.

This work underscores the potential of base metal catalysis in olefin metathesis, a transformation previously thought to be predominantly the domain of 4d and 5d metal species. Importantly, the authors show how careful choice of ancillary pincer and phosphine components can stabilize reactive intermediate species, allowing the observation of key snapshots along the metathesis pathway.

This study not only expands our understanding of the mechanisms by which first-row metal compounds activate olefins but also paves the way for future exploration of base metal-catalyzed olefin metathesis. The ability to employ iron, a non-precious, abundant, and environmentally friendly metal, to catalyze a transformation previously thought to be the purview of heavy metal species holds promise for developing more sustainable and cost-effective catalytic strategies.

Overall, this manuscript provides a sophisticated and insightful view into the mechanisms of iron-catalyzed olefin metathesis and highlights the potential for designing base metal catalyzers to perform challenging bond-forming reactions with high selectivity and under milder conditions. It makes a valuable contribution to the growing body of knowledge in base metal catalysis and organometallic mechanisms. However, the results are still not as efficient or selective as those with the well-established Ru-, Mo-, and W-based catalysts.

We apologize for the omission.