School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, United Kingdom.
Inorg Chem. 2023 Jun 19;62(24):9300-9305. doi: 10.1021/acs.inorgchem.3c01667. Epub 2023 Jun 7.
Solid "[Au]" (H = 3-[pyrid-2-yl]-5-butyl-1-pyrazole) can be crystallized as cyclic [Au(μ-)] and [Au(μ-)] clusters from different solvents. The crystalline tetramer contains a square Au 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 AgBF to [Au] yields [AgAu(μ-)][BF], where two edges of the Au square are spanned by Ag ions via metallophilic Ag···Au contacts. Treatment of [Au] with [Cu(NCMe)]PF affords the metalloligand helicate [CuAu(μ-)][PF], via oxidation of the copper and partial fragmentation of the cluster.
固态“Au”可以从不同溶剂中结晶为环状[Au(μ-)]和[Au(μ-)]簇。晶体四聚体包含一个正方形 Au 核，配体取代基具有 HT:TH:TH:HT 的排列方式，这使得簇预先组织成通过其悬垂吡啶基螯合额外金属离子。向[Au]中加入 0.5 当量的 AgBF 生成[AgAu(μ-)][BF]，其中 Au 正方形的两条边通过金属亲合 Ag···Au 接触由 Ag 离子跨越。用[Cu(NCMe)]PF 处理[Au]，通过铜的氧化和部分簇的碎裂，得到金属配合物螺旋[CuAu(μ-)][PF]。
