A ten-electron (10e) thiolate-protected Au29(SR)19 cluster: structure prediction and a ‘gold-atom insertion, thiolate-group elimination’ mechanism

Abstract

The atomic structure of a ten-electron (10e) thiolate-protected gold cluster, denoted as Au₂₉(SR)₁₉, was theoretically predicted. Based on the prediction of the atomic structure of the 10e Au₂₉(SR)₁₉ cluster, we proposed a novel ‘gold-atom insertion, thiolate-group elimination’ mechanism to understand the structural evolution of the face-centered-cubic (fcc) thiolate-protected gold clusters. The key step of structural evolution from Au₂₈(SR)₂₀ to Au₂₉(SR)₁₉ and then to the Au₃₀(SR)₁₈ cluster, i.e. the growth of triangle-Au₃ units in the gold cores, is understood from the first insertion of an exterior Au(0) atom into the ligand shell and then cleavage of μ₃-SR groups.