Work

Nucleophilic Gallyl Anions Enable Ga─Au Bimetallic Ammonia Activation

Year: 2026

Type: article

Abstract: 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 3 and H 2 O, and extended to MeNH 2 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.

Source: Angewandte Chemie International Edition

DOI: 10.1002/anie.7183298

Authors: Hellen Videa, Keelan M. Byrne, Tobias Krämer, Antonio J. Martínez‐Martínez

Institutions: Universidad de Huelva, National University of Ireland, Maynooth, Trinity College Dublin

Language: English

Topic: Synthesis and characterization of novel inorganic/organometallic compounds

Subfield: Inorganic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $5,510