ArticleJournal of the American Chemical Society2025
3-Center-3-Electron σ-Adduct Enables Silyl Radical Transfer below the Minimum Barrier for Silyl Radical Formation.
Article in Journal of the American Chemical Society, 2025. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 3 papers.
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Who cites it
3 citing papers in PubMed.
- Identification of an air- and moisture-tolerant MOF-based C-H amination catalyst.Chemical communications (Cambridge, England) · 2026Article
- Click Heterogenization of Phosphines Furnishes Recyclable Hydroformylation Catalysts that Reproduce Homogeneous Performance.Journal of the American Chemical Society · 2025Article
- Pericyclic Umpolung in a Catalytic Asymmetric Diels-Alder Reaction of Tropone with Enol Ethers.Journal of the American Chemical Society · 2025Article
Corrections and comments
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Authors and funding
10 authors.
Funding
No grant is acknowledged in the PubMed record.
Abstract
Transition-metal-catalyzed cleavage of the Si-H bond in silanes to yield silyl radicals requires substantial amounts of energy, which are commonly supplied by photons. For Rh(II) porphyrins, efficient hydrosilylation catalysis becomes accessible only upon site isolation in a metal-organic framework (MOF), and the formation of free silyl radicals likewise requires irradiation. Within the MOF, however, an uncommonly facile direct silyl radical transfer to olefin substrates is also possible, which makes thermal olefin hydrosilylation accessible at room temperature. The ability of MOF-supported Rh(II) metalloradicals to furnish an unprecedented 3-center-3-electron (3c-3e) Rh(II)-silane σ-adduct enables the assembly of a tricomponent transition state that is comprised of Rh(II), silane, and ethylene. The tricomponent transition state bypasses the high-energy silyl radical species and enables silyl radical transfer with an activation free energy ∼15 kcal·mol
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Registered trials
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