Atom-Precise Organometallic Zinc Clusters

The bottom‐up synthesis of organometallic zinc clusters is described. The cation {[Zn10](Cp*)6Me}+ (1) is obtained by reacting [Zn2Cp*2] with [FeCp2][BAr4F] in the presence of ZnMe2. In the presence of suitable ligands, the high reactivity of 1 enables the controlled ion of single Zn units, providing access to the lower‐nuclearity clusters {[Zn9](Cp*)6} (2) and {[Zn8](Cp*)5(tBuNC)3}+ (3). According to DFT calculations, 1 and 2 can be described as closed‐shell species that are electron‐deficient in terms of the Wade–Mingos rules because the apical ZnCp* units that constitute the cluster cage do not have three, but only one, frontier orbitals available for cluster bonding. Zinc behaves flexibly in building the skeletal metal–metal bonds, sometimes providing one major frontier orbital (like Group 11 metals) and sometimes providing three frontier orbitals (like Group 13 elements). The bottom‐up wet chemical synthesis of the ligand‐protected oligonuclear clusters {[Zn10](Cp*)6Me}+, {[Zn9](Cp*)6}, and {[Zn8](Cp*)5(tBuNC)3)}+ is described. According to the Wade–Mingos rules, these zinc clusters are electron‐deficient; quantum‐chemical calculations reveal this to be due to the lack of π‐type frontier orbitals on the apical ZnCp* units for cluster bonding.