Synthesis and Structure of a Hexameric Silver and Tetrameric Gold Aminopyridinates

4-Methyl-2-((trimethylsilyl)amino)pyridine (Ap(TMS)H) was synthesized via a salt metathesis reaction. Lithiation of Ap(TMS)H with n-BULi afforded the transmetallation agent [(Ap(TMS))(2)Li-2(OEt2)(2)] (1) which was structurally characterized. Reaction of 1 with AgCl and [AuCl(tht)] (tht = tetrahydrothiophene) at low temperatures in THF yielded homoleptic aminopyridinates of the heavier group 11 metals, namely [(Ap(TMS))(6)AG(6)] (2) and [(Ap(TMS))(4)Au-4] (3a and b) after work-up in hexane. All compounds were characterized by X-ray crystal structure analysis. The quality of the structure determination of 3a allows establishing the connectivity only. The lithium complex 1 shows the expected structure from analogous compounds. The hexameric silver compound shows a new structural motif for silver aminopyridinates. The six-membered ring of silver atoms has a chair conformation. Compounds 3a and b are the first homoleptic gold aminopyridinates and exhibit a rhombic arrangement of the four gold atoms.