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Banh H, Dilchert K, Schulz C, et al. Atom-Precise Organometallic Zinc Clusters. Angew Chem Int Ed Engl. 2016;55(10):3285-9doi: 10.1002/anie.201510762.
Banh, H., Dilchert, K., Schulz, C., Gemel, C., Seidel, R. W., Gautier, R., Kahlal, S., Saillard, J. Y., & Fischer, R. A. (2016). Atom-Precise Organometallic Zinc Clusters. Angewandte Chemie (International ed. in English), 55(10), 3285-9. https://doi.org/10.1002/anie.201510762
Banh, Hung, et al. "Atom-Precise Organometallic Zinc Clusters." Angewandte Chemie (International ed. in English) vol. 55,10 (2016): 3285-9. doi: https://doi.org/10.1002/anie.201510762
Banh H, Dilchert K, Schulz C, Gemel C, Seidel RW, Gautier R, Kahlal S, Saillard JY, Fischer RA. Atom-Precise Organometallic Zinc Clusters. Angew Chem Int Ed Engl. 2016 Mar 01;55(10):3285-9. doi: 10.1002/anie.201510762. Epub 2016 Feb 05. PMID: 26846901.
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Angew Chem Int Ed Engl. 2016 Mar 01;55(10):3285-9. doi: 10.1002/anie.201510762. Epub 2016 Feb 05.

Atom-Precise Organometallic Zinc Clusters.

Angewandte Chemie (International ed. in English)

Hung Banh, Katharina Dilchert, Christine Schulz, Christian Gemel, Rüdiger W Seidel, Régis Gautier, Samia Kahlal, Jean-Yves Saillard, Roland A Fischer

Affiliations

  1. Anorganische Chemie II - Organometallics and Materials, Fakultät für Chemie und Biochemie, Ruhr-Universität Bochum, 44780, Bochum, Germany.
  2. Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-ENSC Rennes, Université de Rennes 1, 35042, Rennes Cedex, France.
  3. Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-ENSC Rennes, Université de Rennes 1, 35042, Rennes Cedex, France. [email protected].
  4. Anorganische Chemie II - Organometallics and Materials, Fakultät für Chemie und Biochemie, Ruhr-Universität Bochum, 44780, Bochum, Germany. [email protected].

PMID: 26846901 DOI: 10.1002/anie.201510762

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).

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords: ELF; Wade-Mingos rules; clusters; density functional calculations; zinc

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