title: Atom-Precise Organometallic Zinc Clusters.
abstract: The bottom-up synthesis of organometallic zinc clusters is described. The cation {[Zn10](Cp*)6 Me}(+) (1) is obtained by reacting [Zn2 Cp*2] with [FeCp2][BAr4 (F)] 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 ((t) BuNC)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).
authors: Anorganische Chemie II - Organometallics and Materials, Fakultät für Chemie und Biochemie, Ruhr-Universität Bochum, 44780, Bochum, Germany.
authors: Hung
authors: H
authors: Banh
authors: Anorganische Chemie II - Organometallics and Materials, Fakultät für Chemie und Biochemie, Ruhr-Universität Bochum, 44780, Bochum, Germany.
authors: Katharina
authors: K
authors: Dilchert
authors: Anorganische Chemie II - Organometallics and Materials, Fakultät für Chemie und Biochemie, Ruhr-Universität Bochum, 44780, Bochum, Germany.
authors: Christine
authors: C
authors: Schulz
authors: Anorganische Chemie II - Organometallics and Materials, Fakultät für Chemie und Biochemie, Ruhr-Universität Bochum, 44780, Bochum, Germany.
authors: Christian
authors: C
authors: Gemel
authors: Anorganische Chemie II - Organometallics and Materials, Fakultät für Chemie und Biochemie, Ruhr-Universität Bochum, 44780, Bochum, Germany.
authors: Rüdiger W
authors: RW
authors: Seidel
authors: Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-ENSC Rennes, Université de Rennes 1, 35042, Rennes Cedex, France.
authors: Régis
authors: R
authors: Gautier
authors: Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-ENSC Rennes, Université de Rennes 1, 35042, Rennes Cedex, France.
authors: Samia
authors: S
authors: Kahlal
authors: Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-ENSC Rennes, Université de Rennes 1, 35042, Rennes Cedex, France. jean-yves.saillard@univ-rennes1.fr.
authors: Jean-Yves
authors: JY
authors: Saillard
authors: Anorganische Chemie II - Organometallics and Materials, Fakultät für Chemie und Biochemie, Ruhr-Universität Bochum, 44780, Bochum, Germany. roland.fischer@rub.de.
authors: Roland A
authors: RA
authors: Fischer
keywords: ELF; Wade-Mingos rules; clusters; density functional calculations; zinc