2023 年 81 巻 p. 20-38
Intermetallics (M1/M2) of abundant metals of very different properties can substitute rare and precious metals for industrial catalysis. A challenge in this context is the atom-precise and -efficient catalyst design at the size regime of ≤ 1 nm, where every metal atom counts. Along these lines of thought we have been developing a novel way to generate libraries of all-hydrocarbon (R*) ligated clusters [M1aM1b](R*)c. These organometallic clusters and superatom complexes are molecular counterparts of the solid state M1/M2 materials. The electronic structure, e.g. open vs. closed ‘superatom shell’, controls stability and reactivity. The libraries are metastable and the hypothesis is that they are loaded with interrelated clusters, elusive and highly reactive ones as well as more accessible but less reactive ones. The chemical control parameters relate to fundamental organometallic reaction networks of nucleation, growth and degradation, to ligand and/or additive association, dissociation, to cluster surface metal-atom site activation by ligand deprotection and to reactions with small molecules. The article is a personal account of a long-time research enterprise on the coordination chemistry of group12/13 metallo-ligands at transition metal centers, and the related mixed-metal cluster chemistry to the emergence of “living libraries” of such clusters.
