Iron-borane catalyzed carbonyl hydroboration and isolation of an iron(I)-ketyl radical.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 41714625.
- Also identified by DOI 10.1038/s41467-026-69500-2 and PMC identifier 13031794.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
Hydroboration of carbonyl compounds has proven a pivotal route to access alcohols and other C1 moieties in recent years. Despite this, iron-based catalyst systems are somewhat limited with very little mechanistic understanding of these systems developed. Here we show that an iron metalloborane complex [{(<sup>iPr</sup>DPB<sup>Ph</sup>)Fe}<sub>2</sub>(μ-1,2-N<sub>2</sub>)] (A) is an efficient pre-catalyst for hydroboration of ketones, cyclic esters and CO<sub>2</sub> with mild conditions. Mechanistic insights reveal a previously unreported direct iron(0)-mediated ligand-to-ligand hydride transfer (LLHT) process is in operation with B-H bond breaking being rate determining, indicating the importance of mechanistic studies on well-known transformations. An iron(I)-benzophenone ketyl radical with a unique S = 1 antiferromagnetic ground state has been isolated and fully characterized.