Ligand-Directed Metallation of a Gold Pyrazolate Cluster

Solid “[AuL]” (HL = 3-[pyrid-2-yl]-5-tertbutyl-1H-pyrazole) can be crystallized as cyclic [Au3(μ-L)3] and [Au4(μ-L)4] clusters from different solvents. The crystalline tetramer contains a square Au4 core with an HT:TH:TH:HT arrangement of ligand substituents, which preorganizes the cluster to chelate to additional metal ions via its pendant pyridyl groups. The addition of 0.5 equiv of AgBF4 to [AuL] yields [Ag2Au4(μ3-L)4][BF4]2, where two edges of the Au4 square are spanned by Ag+ ions via metallophilic Ag···Au contacts. Treatment of [AuL] with [Cu(NCMe)4]PF6 affords the metalloligand helicate [Cu2Au2(μ-L)4][PF6]2, via oxidation of the copper and partial fragmentation of the cluster.