A Stable Neutral Radical in the Coordination Sphere of Aluminum

Bin Li; Subrata Kundu; A. Claudia Stückl; Hongping Zhu; Helena Keil; Regine Herbst-Irmer; Dietmar Stalke; Brigitte Schwederski; Wolfgang Kaim; Diego M. Andrada; Gernot Frenking; Herbert W. Roesky

doi:10.1002/anie.201609101

A Stable Neutral Radical in the Coordination Sphere of Aluminum

Bin Li, Subrata Kundu, A. Claudia Stückl, Hongping Zhu, Helena Keil, Regine Herbst-Irmer, Dietmar Stalke, Brigitte Schwederski, Wolfgang Kaim, Diego M. Andrada, Gernot Frenking, Herbert W. Roesky

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

61 Scopus citations

Abstract

The neutral radical (Me₂-cAAC)₂AlCl₂(2) is stabilized by cyclic (alkyl)(amino)carbenes (cAACs). Complex 2 was synthesized by reduction of the Me₂-cAAC:→AlCl₃(1) adduct with KC₈in the presence of another equivalent of Me₂-cAAC. The crystal structure of 2 shows that the Al−C bond lengths of the two carbenes bound to the Al center are considerably different, which is likely the result of intermolecular interactions. Quantum-chemical calculations from the gas phase give an equilibrium structure with identical Al−C bond lengths. Compound 2 exhibits monoradical character, which was confirmed by EPR measurements. A bonding analysis indicates that the unpaired electron resides mainly at the carbene carbon atoms. Compound 2 is an example for an unusual neutral Al radical.

Original language	English
Pages (from-to)	397-400
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	56
Issue number	1
DOIs	https://doi.org/10.1002/anie.201609101
State	Published - 2 Jan 2017
Externally published	Yes

Keywords

aluminum radicals
bonding analysis
cyclic alkyl(amino) carbenes
theoretical calculations

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title = "A Stable Neutral Radical in the Coordination Sphere of Aluminum",

abstract = "The neutral radical (Me2-cAAC)2AlCl2(2) is stabilized by cyclic (alkyl)(amino)carbenes (cAACs). Complex 2 was synthesized by reduction of the Me2-cAAC:→AlCl3(1) adduct with KC8in the presence of another equivalent of Me2-cAAC. The crystal structure of 2 shows that the Al−C bond lengths of the two carbenes bound to the Al center are considerably different, which is likely the result of intermolecular interactions. Quantum-chemical calculations from the gas phase give an equilibrium structure with identical Al−C bond lengths. Compound 2 exhibits monoradical character, which was confirmed by EPR measurements. A bonding analysis indicates that the unpaired electron resides mainly at the carbene carbon atoms. Compound 2 is an example for an unusual neutral Al radical.",

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AU - Li, Bin

AU - Kundu, Subrata

AU - Stückl, A. Claudia

AU - Zhu, Hongping

AU - Keil, Helena

AU - Herbst-Irmer, Regine

AU - Stalke, Dietmar

AU - Schwederski, Brigitte

AU - Kaim, Wolfgang

AU - Andrada, Diego M.

AU - Frenking, Gernot

AU - Roesky, Herbert W.

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N2 - The neutral radical (Me2-cAAC)2AlCl2(2) is stabilized by cyclic (alkyl)(amino)carbenes (cAACs). Complex 2 was synthesized by reduction of the Me2-cAAC:→AlCl3(1) adduct with KC8in the presence of another equivalent of Me2-cAAC. The crystal structure of 2 shows that the Al−C bond lengths of the two carbenes bound to the Al center are considerably different, which is likely the result of intermolecular interactions. Quantum-chemical calculations from the gas phase give an equilibrium structure with identical Al−C bond lengths. Compound 2 exhibits monoradical character, which was confirmed by EPR measurements. A bonding analysis indicates that the unpaired electron resides mainly at the carbene carbon atoms. Compound 2 is an example for an unusual neutral Al radical.

AB - The neutral radical (Me2-cAAC)2AlCl2(2) is stabilized by cyclic (alkyl)(amino)carbenes (cAACs). Complex 2 was synthesized by reduction of the Me2-cAAC:→AlCl3(1) adduct with KC8in the presence of another equivalent of Me2-cAAC. The crystal structure of 2 shows that the Al−C bond lengths of the two carbenes bound to the Al center are considerably different, which is likely the result of intermolecular interactions. Quantum-chemical calculations from the gas phase give an equilibrium structure with identical Al−C bond lengths. Compound 2 exhibits monoradical character, which was confirmed by EPR measurements. A bonding analysis indicates that the unpaired electron resides mainly at the carbene carbon atoms. Compound 2 is an example for an unusual neutral Al radical.

KW - aluminum radicals

KW - bonding analysis

KW - cyclic alkyl(amino) carbenes

KW - theoretical calculations

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A Stable Neutral Radical in the Coordination Sphere of Aluminum

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Keywords

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