Roland A. Fischer, Inorganic Chemistry II—Organometallics and Materials, Faculty of Chemistry and Biochemistry, Ruhr University Bochum, 44780 Bochum (Germany)

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Hung Banh,

Hung Banh

Inorganic Chemistry II—Organometallics and Materials, Faculty of Chemistry and Biochemistry, Ruhr University Bochum, 44780 Bochum (Germany)

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Katharina Dilchert,

Katharina Dilchert

Inorganic Chemistry II—Organometallics and Materials, Faculty of Chemistry and Biochemistry, Ruhr University Bochum, 44780 Bochum (Germany)

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Prof. Dr. Roland A. Fischer,

Corresponding Author

Prof. Dr. Roland A. Fischer

[email protected]

Inorganic Chemistry II—Organometallics and Materials, Faculty of Chemistry and Biochemistry, Ruhr University Bochum, 44780 Bochum (Germany)

Gernot Frenking, Department of Chemistry, Philipps University Marburg, 35032 Marburg (Germany)

Roland A. Fischer, Inorganic Chemistry II—Organometallics and Materials, Faculty of Chemistry and Biochemistry, Ruhr University Bochum, 44780 Bochum (Germany)

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Dr. Kerstin Freitag,

Dr. Kerstin Freitag

Inorganic Chemistry II—Organometallics and Materials, Faculty of Chemistry and Biochemistry, Ruhr University Bochum, 44780 Bochum (Germany)

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Dr. Christian Gemel,

Dr. Christian Gemel

Inorganic Chemistry II—Organometallics and Materials, Faculty of Chemistry and Biochemistry, Ruhr University Bochum, 44780 Bochum (Germany)

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Dr. Paul Jerabek,

Dr. Paul Jerabek

Department of Chemistry, Philipps University Marburg, 35032 Marburg (Germany)

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Prof. Dr. Iris M. Oppel,

Prof. Dr. Iris M. Oppel

Institut of Inorganic Chemistry, RWTH Aachen University, 52056 Aachen (Germany)

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Dr. Rüdiger W. Seidel,

Dr. Rüdiger W. Seidel

Inorganic Chemistry II—Organometallics and Materials, Faculty of Chemistry and Biochemistry, Ruhr University Bochum, 44780 Bochum (Germany)

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Prof. Dr. Gernot Frenking,

Corresponding Author

Prof. Dr. Gernot Frenking

[email protected]

Department of Chemistry, Philipps University Marburg, 35032 Marburg (Germany)

Gernot Frenking, Department of Chemistry, Philipps University Marburg, 35032 Marburg (Germany)

Roland A. Fischer, Inorganic Chemistry II—Organometallics and Materials, Faculty of Chemistry and Biochemistry, Ruhr University Bochum, 44780 Bochum (Germany)

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Hung Banh,

Hung Banh

Inorganic Chemistry II—Organometallics and Materials, Faculty of Chemistry and Biochemistry, Ruhr University Bochum, 44780 Bochum (Germany)

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Katharina Dilchert,

Katharina Dilchert

Inorganic Chemistry II—Organometallics and Materials, Faculty of Chemistry and Biochemistry, Ruhr University Bochum, 44780 Bochum (Germany)

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Prof. Dr. Roland A. Fischer,

Corresponding Author

Prof. Dr. Roland A. Fischer

[email protected]

Inorganic Chemistry II—Organometallics and Materials, Faculty of Chemistry and Biochemistry, Ruhr University Bochum, 44780 Bochum (Germany)

Gernot Frenking, Department of Chemistry, Philipps University Marburg, 35032 Marburg (Germany)

Roland A. Fischer, Inorganic Chemistry II—Organometallics and Materials, Faculty of Chemistry and Biochemistry, Ruhr University Bochum, 44780 Bochum (Germany)

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First published: 12 February 2015

https://doi.org/10.1002/anie.201410737

Citations: 88

^†

This work was funded by the Deutsche Forschungsgemeinschaft (individual grant Fi-502/23-2) and by RESOLV (EXC 1069). The dissertation project of K.F. was supported by the German Chemical Industry Fund (https://vci.de/fonds) and the Ruhr University Research School (http://www.research-school.rub.de/). H.B. is grateful for a scholarship of the German Chemical Industry Fund.

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Graphical Abstract

Bold as brass: The bonding situations of the Cp* ligand-protected clusters [Zn₃]⁺ (1) and [Zn₂Cu] (2) were investigated by quantum chemical calculations revealing a high degree of σ-aromaticity similar to the trihydrogen ion [H₃]⁺. The new species serve as molecular building units of Cu_nZn_m nanobrass clusters as indicated by liquid-injection field desorption ionization (LIFDI) mass spectrometry.

Abstract

The triangular clusters [Zn₃Cp*₃]⁺ and [Zn₂CuCp*₃] were obtained by addition of the in situ generated, electrophilic, and isolobal species [ZnCp*]⁺ and [CuCp*] to Carmona’s compound, [Cp*ZnZnCp*], without splitting the ZnZn bond. The choice of non-coordinating fluoroaromatic solvents was crucial. The bonding situations of the all-hydrocarbon-ligand-protected clusters were investigated by quantum chemical calculations revealing a high degree of σ-aromaticity similar to the triatomic hydrogen ion [H₃]⁺. The new species serve as molecular building units of Cu_nZn_m nanobrass clusters as indicated by LIFDI mass spectrometry.

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Volume54, Issue14

March 27, 2015

Pages 4370-4374

The σ-Aromatic Clusters [Zn₃]⁺ and [Zn₂Cu]: Embryonic Brass^†

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The σ-Aromatic Clusters [Zn3]+ and [Zn2Cu]: Embryonic Brass†

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The σ-Aromatic Clusters [Zn₃]⁺ and [Zn₂Cu]: Embryonic Brass^†