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Abstract Herein, we describe a new strategy for the carbonylation of alkyl halides with different nucleophiles to generate valuable carbonyl derivatives under visible light irradiation. This method is mild, robust, highly selective, and proceeds under metal‐free conditions to prepare a range of structurally diverse esters and amides in good to excellent yields. In addition, we highlight the application of this activation strategy for13C isotopic incorporation. We propose that the reaction proceeds by a photoinduced reduction to afford carbon‐centered radicals from alkyl halides, which undergo subsequent single electron‐oxidation to form a carbocationic intermediate. Carbon monoxide is trapped by the carbocation to generate an acylium cation, which can be attacked by a series of nucleophiles to give a range of carbonyl products.
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This content will become publicly available on March 24, 2026
Bis(iminoxolene)iridium Anion and Alkyls: How Does Ligand Redox Noninnocence Interface with Oxidative Addition?
The bis(iminoxolene) complex (Diso)2IrCl (Diso = N-(2,6-diisopropylphenyl)-4,6-di-tert-butyl-2-imino-o-benzoquinone) is reduced by two equivalents of sodium naphthalenide to give square planar, diamagnetic Na[(Diso)2Ir]. The anionic iridium center acts as a nucleophile to primary and secondary alkyl and allyl halides to give square pyramidal iridium alkyls. Benzoyl chloride reacts to give an iridium benzoyl complex. Organoiridium complexes are also formed by reaction of (Diso)2IrCl with Grignard reagents, and treatment with acetone in the presence of base gives the 1 carbon-bonded enolate complex (Diso)2IrCH2COCH3. The solid-state structures of the primary alkyls show significant inclinations of the iridium-carbon bond away from the twofold axis of the square pyramid, apparently for steric reasons. The relative reactivity of substrates and exclusive formation of (Diso)2Ir(5-hexenyl) from 1-bromo-5-hexene indicates that primary alkyl halides react by an SN2 mechanism. Structural data suggest that the oxidative addition is about 70% metal centered, consistent with nucleophilic behavior that is analogous to that of other square planar group 9 anions.
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- PAR ID:
- 10590720
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Organometallics
- Volume:
- 44
- Issue:
- 6
- ISSN:
- 0276-7333
- Page Range / eLocation ID:
- 760 to 775
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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