biostudies-literatureUnknown147(36)Herle DLow-valent cadmium compounds have remained largely unexplored as electron reservoirs, with no precedent for their use in reduction or bond activation chemistry. Here, we address this gap by integrating low-valent aluminum into the cadmium coordination sphere. Aluminylene insertion into Cd{N(TMS)2}2 affords bi- and trimetallic cadmium aluminyls 1 and 2, featuring covalent yet tunable Al-Cd bonding. While 1 is irreversibly formed, 2 exhibits dynamic reactivity, enabling reversible [AlCp*]0 transfer─a rare and previously undocumented feature in heterobimetallic aluminum chemistry. Acting as a thermodynamically stable yet chemically reactive surrogate for free Al(I), 2 enables selective Al(I) shuttling to B, Cd, Zn, and Ag subJournal of the American Chemical Society33315-33323https://www.ebi.ac.uk/biostudies/studies/S-EPMC12426937biostudies-literatureFunctional Al/Cd Heterometallics─From Controlled Al(I) Transfer to Nucleophilic Transfer of Cadmium Ions.PMC12426937Herle DSommer SDankert FfalseFunctional Al/Cd Heterometallics─From Controlled Al(I) Transfer to Nucleophilic Transfer of Cadmium Ions.Low-valent cadmium compounds have remained largely unexplored as electron reservoirs, with no precedent for their use in reduction or bond activation chemistry. Here, we address this gap by integrating low-valent aluminum into the cadmium coordination sphere. Aluminylene insertion into Cd{N(TMS)2}2 affords bi- and trimetallic cadmium aluminyls 1 and 2, featuring covalent yet tunable Al-Cd bonding. While 1 is irreversibly formed, 2 exhibits dynamic reactivity, enabling reversible [AlCp*]0 transfer─a rare and previously undocumented feature in heterobimetallic aluminum chemistry. Acting as a thermodynamically stable yet chemically reactive surrogate for free Al(I), 2 enables selective Al(I) shuttling to B, Cd, Zn, and Ag sub2025-01-01T00:00:00Z2025 Sep2026-06-01T12:05:05.145Z2026-04-08T12:05:59.448ZS-EPMC124269374085407310.1021/jacs.5c12746