Unveiling the Unique Reactivity of Anionic Mn(I) Complexes via Metal–Ligand Cooperation: Nucleophilic Attack on C(sp3)–X Bonds
Metal–ligand cooperation (MLC) has emerged as a pivotal strategy for the catalytic activation of small molecules within both synthetic and biological arenas. Leveraging this approach, a suite of potent catalytic reactionsencompassing hydrogenation, hydroelementation, and dehydrogenative processesh...
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Veröffentlicht in: | Journal of the American Chemical Society 2024-10, Vol.146 (39), p.26649-26656 |
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Format: | Artikel |
Sprache: | eng |
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Zusammenfassung: | Metal–ligand cooperation (MLC) has emerged as a pivotal strategy for the catalytic activation of small molecules within both synthetic and biological arenas. Leveraging this approach, a suite of potent catalytic reactionsencompassing hydrogenation, hydroelementation, and dehydrogenative processeshave been realized, with notable advances in manganese catalysis in recent years. However, the activation of alkyl halides by Mn complexes, which typically requires strong reductants to form Mn(–I) complexes that are incompatible with standard cross-coupling conditions, remains a significant challenge. This limitation underscores the urgent need to investigate alternative methods for activating C(sp3)–X bonds using higher valence state Mn complexes. In response to this challenge, we present the synthesis, characterization, and reactivity of a new anionic Mn(I) complex featuring a redox-active dianionic ligand that induces multiple MLC functionalities. We have discovered an innovative mechanism of MLC, characterized by a single ligand transferring two electrons to the metal center. This novel process facilitates an orbital-symmetry-allowed nucleophilic attack on C(sp3)–X bonds, preserving manganese’s oxidative state at +1. To the best of our knowledge, this is the first instance where the MLC strategy via a two-electron transfer process has been utilized to execute an SN2 nucleophilic attack at a C(sp3)–X bond by a relatively electron-deficient metal center like Mn(I). Additionally, the dianionic ligand of the anionic Mn(I) complex exhibits ambident nucleophilicity by reacting with different electrophiles, further highlighting its versatile reactivity. |
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ISSN: | 0002-7863 1520-5126 1520-5126 |
DOI: | 10.1021/jacs.4c01683 |