Unusual reactivity of dithiol protected clusters in comparison to monothiol protected clusters: studies using Ag₅₁(BDT)₁₉(TPP)₃and Ag₂₉(BDT)₁₂(TPP)₄

Abstract

We report the synthesis and unique reactivity of a new green dithiol protected cluster (DTPC), Ag₅₁(BDT)₁₉(TPP)₃ (BDT and TPP are 1,3-benzenedithiol and triphenylphosphine, respectively). The cluster composition was confirmed by electrospray ionization (ESI) and matrix-assisted laser desorption ionization (MALDI) mass spectrometric studies as well as by other supporting data. Surprisingly, the chemical reactivity between this DTPC and Au₂₅(SR)₁₈ involves only metal ion exchange in Au₂₅(SR)₁₈ without any ligand exchange, while reactions between monothiol protected clusters (MTPCs) show both metal and ligand exchange, an example being the reaction between Ag₂₅DMBT₁₈ and Au₂₅PET₁₈ (where DMBT and PET are 2,4-dimethylbenzenethiol and phenylethanethiol, respectively). The conclusions have been confirmed by the reaction of another DTPC, Ag₂₉(BDT)₁₂(TPP)₄ with Au₂₅BT₁₈ (where BT corresponds to butanethiol) in which only metal exchange happens in Au₂₅BT₁₈. We also show the conversion of Ag₅₁(BDT)₁₉(TPP)₃ to Ag₂₉(BDT)₁₂(TPP)₄ in the presence of a second monothiol, DMBT which does not get integrated into the product cluster. This is completely different from the previous understanding wherein the reaction between MTPCs and a second thiol leads to either mixed thiol protected clusters with the same core composition or a completely new cluster core protected with the second thiol. The present study exposes a new avenue of research for monolayer protected clusters, which in turn will give additional impetus to explore the chemistry of DTPCs.