Au₃₀(P<i>ⁱ</i>Pr₂<i>ⁿ</i>Bu)₁₂Cl₆—An Open Cluster Provides Insight into the Influence of the Sterical Demand of the Phosphine Ligand in the Formation of Metalloid Gold Clusters

Abstract

Phosphine-stabilized gold clusters are an important subgroup of metalloid gold cluster compounds and are important model compounds for nanoparticles. Although there are numerous gold clusters with different phosphine ligands, the effect of phosphine on cluster formation and structure remains unclear. While the linear alkyl-substituted phosphine gold chlorides result in a Au32 cluster, the bulky tBu3P leads to a Au20 cluster. The reduction of (iPr2nBuP)AuCl, with the steric demand of the phosphine ligand between the mentioned phosphines, results in the successful synthesis and crystallization of a new metalloid gold cluster, Au30(PiPr2nBu)12Cl6. Its structure is similar to the Au32 cluster but with two missing AuCl units. The UV/Vis studies and quantum chemical calculations show the similarities between the two clusters and the influence of the phosphine ligand in the synthesis of metalloid gold clusters.

Keywords

• gold cluster
• cluster formation
• phosphine ligand
• X-ray structure
• cluster transformation
• steric effect