ArticleAngewandte Chemie (International ed. in English)2026
Nucleophilic Gallyl Anions Enable Ga─Au Bimetallic Ammonia Activation.
Article in Angewandte Chemie (International ed. in English), 2026. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Not yet cited in PubMed.
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Abstract
Controlling the reactivity of low-valent main-group nucleophiles in small-molecule activation remains a significant challenge. Here, we report the synthesis of a family of charge-delocalized β-diketiminate gallyl anions, accessible across the Li-Cs series, whose aggregation and ion pairing can be tuned to furnish a cation-gated gallium(I) nucleophilic platform. Only the cesium crown-encapsulated derivative forms a truly separated ion pair (SIP) that exhibits clean nucleophilic reactivity toward (IPr)AuCl to generate an unsupported Ga─Au bimetallic complex, isolable, and structurally authenticated. Coordination at Au enhances the Lewis acidity at gallium(I), enabling cooperative N─H and O─H σ-bond activation under mild conditions via a substrate-assisted proton-shuttle pathway. This reactivity, exemplified by NH
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