Atom-Precise Organometallic Zinc Clusters

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

doi:10.1002/anie.201510762

Atom-Precise Organometallic Zinc Clusters

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

Research output: Contribution to journal › Article › peer-review

17 Scopus citations

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][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(^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).

Original language	English
Pages (from-to)	3285-3289
Number of pages	5
Journal	Angewandte Chemie International Edition in English
Volume	55
Issue number	10
DOIs	https://doi.org/10.1002/anie.201510762
State	Published - 1 Mar 2016
Externally published	Yes

Keywords

ELF
Wade-Mingos rules
clusters
density functional calculations
zinc

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title = "Atom-Precise Organometallic Zinc Clusters",

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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doi = "10.1002/anie.201510762",

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AU - Banh, Hung

AU - Dilchert, Katharina

AU - Schulz, Christine

AU - Gemel, Christian

AU - Seidel, Rüdiger W.

AU - Gautier, Régis

AU - Kahlal, Samia

AU - Saillard, Jean Yves

AU - Fischer, Roland A.

PY - 2016/3/1

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N2 - 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).

AB - 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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Atom-Precise Organometallic Zinc Clusters

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