@article{10272/28452,
year = {2026},
url = {https://hdl.handle.net/10272/28452},
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 NH3 and H2 O, and extended to MeNH2 and MeOH, is inaccessible to the free gallyl anions. These findings define a new gallium-based nucleophilic platform for exploiting bimetallic cooperation in small-molecule bond activation.},
organization = {The authors would like to thank the Spanish Ministerio de Ciencia e Innovación MICIN/AEI/10.13039/501100011033 (PID2022-142270OB- I00), MICIN/NextGenerationEU/PRTR (CNS2022-136087), the European Research and Development Fund (ERDF) and the University of Huelva (EPIT1442023) for funding, and the Spanish Research State Agency (AEI) for a Ramón y Cajal Research Contract (RYC-2017-21783 to A.J.M-M.). The authors wish to acknowledge the teams at the Irish Centre for High-End Computing (ICHEC) and LuxProvide for the provision of computational facilities and technical support. K.M.B. thanks the Irish Research Council for funding under grant number GOIPG/2022/470. T.K. thanks the RSC for a Research Enablement Grant (E21-7643704122). Funding for open access was provided by the University of Huelva (CBUA).},
publisher = {Wiley},
title = {Nucleophilic Gallyl Anions Enable Ga-Au Bimetallic Ammonia Activation},
doi = {10.1002/anie.7183298},
author = {Videa, Hellen and Byrne, Keelan M. and Krämer, Tobias and Martínez Martínez, Antonio Jesús},
}