Atom‐Precise Organometallic Zinc Clusters |
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| Authors: | Hung Banh Katharina Dilchert Christine Schulz Dr Christian Gemel Dr Rüdiger W Seidel Dr Régis Gautier Dr Samia Kahlal Prof Dr Jean‐Yves Saillard Prof Dr Roland A Fischer |
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| Institution: | 1. Anorganische Chemie II - Organometallics and Materials, Fakult?t für Chemie und Biochemie, Ruhr-Universit?t Bochum, Bochum, Germany;2. Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-ENSC Rennes, Université de Rennes 1, Rennes Cedex, France |
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| Abstract: | 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 abstraction 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). |
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| Keywords: | clusters density functional calculations ELF Wade– Mingos rules zinc |
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