Aufsatz
Homodinuclear Rhˡ and Irˡ Complexes Derived from Imidazolium-Benzimidazolates
Homodinuclear Rhˡ and Irˡ Complexes Derived from Imidazolium-Benzimidazolates
Dedicated to Prof. Christoph Janiak on the Occasion of his 60th Birthday
Zusammenfassung
The reactions of [M(μ-Cl)(COD)]2 (M=Rh, Ir) with the conjugated mesomeric betaines 2-(3-methyl-1-imidazolium)-benzimidazolate (1aH), 2-(3-isopropyl-1-imidazolium)-benzimidazolate (1bH) and 2-(3-tert-butyl-1-imidazolium)-benzimidazolate (1cH) in equilibrium with their carbenic tautomers 1’aH, 1’bH and 1’cH were investigated. In the case of 1aH and 1bH, the homodinuclear complexes [MCl(COD){M(μ-1’a)(COD)}] and [MCl(COD){M(μ-1’b)(COD)}] were obtained, whose anionic NHC ligand 1’a− or 1’b− bridges the metal centres in a κ1N : κ1N mode, while binding the M(COD) moiety in a C,N-chelating mode. For M=Ir, [IrCl(COD){Ir(μ-1’’b)(COD)}] containing the “abnormal” NHC isomer 1’’b− was observed as a side product. In the case of 1’cH, [{RhCl(COD)}2(μ-1cH)] containing a κ1N : κ1N benzimidazolato ligand was obtained for M=Rh, while for M=Ir the reaction furnished [IrCl(COD){Ir(μ-1’’c)(COD)}], which contains the anionic “abnormal” NHC ligand 1’’c−. This difference in behaviour is rationalised by the propensity of iridium(I) for oxidative addition, which in the present case involves a C−H bond of the dangling formamidium unit of [{IrCl(COD)}2(μ-1cH)] to afford [IrICl(COD){IrIIIHCl(μ-1’’c)(COD)}], followed by reductive elimination of HCl. The crystal structures of the new complexes were determined by single-crystal X-ray diffraction, except for [IrCl(COD){Ir(μ-1’a)(COD)}], where by serendipity the closely related mononuclear complex [Ir(1’a)(COD)] was structurally characterised instead.
Zitierform
In: Zeitschrift für anorganische und allgemeine Chemie (ZAAC) = Journal of inorganic and general chemistry Volume 647 / Issue 11 (2020-11-19) , S. 1173-1181 ; eissn:1521-3749Förderhinweis
Gefördert im Rahmen des Projekts DEALZitieren
@article{doi:10.17170/kobra-202106094099,
author={Kureja, Kunal and Zinke, Julian and Bruhn, Clemens and Siemeling, Ulrich},
title={Homodinuclear Rhˡ and Irˡ Complexes Derived from Imidazolium-Benzimidazolates},
journal={Zeitschrift für anorganische und allgemeine Chemie (ZAAC) = Journal of inorganic and general chemistry},
year={2020}
}
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2021-06-17T10:18:34Z 2021-06-17T10:18:34Z 2020-11-19 doi:10.17170/kobra-202106094099 http://hdl.handle.net/123456789/12934 Gefördert im Rahmen des Projekts DEAL eng Namensnennung 4.0 International http://creativecommons.org/licenses/by/4.0/ carbenes coordination modes Iridium; Rhodium x-ray diffraction 540 Homodinuclear Rhˡ and Irˡ Complexes Derived from Imidazolium-Benzimidazolates Aufsatz The reactions of [M(μ-Cl)(COD)]2 (M=Rh, Ir) with the conjugated mesomeric betaines 2-(3-methyl-1-imidazolium)-benzimidazolate (1aH), 2-(3-isopropyl-1-imidazolium)-benzimidazolate (1bH) and 2-(3-tert-butyl-1-imidazolium)-benzimidazolate (1cH) in equilibrium with their carbenic tautomers 1’aH, 1’bH and 1’cH were investigated. In the case of 1aH and 1bH, the homodinuclear complexes [MCl(COD){M(μ-1’a)(COD)}] and [MCl(COD){M(μ-1’b)(COD)}] were obtained, whose anionic NHC ligand 1’a− or 1’b− bridges the metal centres in a κ1N : κ1N mode, while binding the M(COD) moiety in a C,N-chelating mode. For M=Ir, [IrCl(COD){Ir(μ-1’’b)(COD)}] containing the “abnormal” NHC isomer 1’’b− was observed as a side product. In the case of 1’cH, [{RhCl(COD)}2(μ-1cH)] containing a κ1N : κ1N benzimidazolato ligand was obtained for M=Rh, while for M=Ir the reaction furnished [IrCl(COD){Ir(μ-1’’c)(COD)}], which contains the anionic “abnormal” NHC ligand 1’’c−. This difference in behaviour is rationalised by the propensity of iridium(I) for oxidative addition, which in the present case involves a C−H bond of the dangling formamidium unit of [{IrCl(COD)}2(μ-1cH)] to afford [IrICl(COD){IrIIIHCl(μ-1’’c)(COD)}], followed by reductive elimination of HCl. The crystal structures of the new complexes were determined by single-crystal X-ray diffraction, except for [IrCl(COD){Ir(μ-1’a)(COD)}], where by serendipity the closely related mononuclear complex [Ir(1’a)(COD)] was structurally characterised instead. open access Kureja, Kunal Zinke, Julian Bruhn, Clemens Siemeling, Ulrich doi:10.1002/zaac.202000394 Carbene Chemische Bindung Iridium Rhodium Röntgenbeugung Dedicated to Prof. Christoph Janiak on the Occasion of his 60th Birthday publishedVersion eissn:1521-3749 Issue 11 Zeitschrift für anorganische und allgemeine Chemie (ZAAC) = Journal of inorganic and general chemistry 1173-1181 Volume 647 false
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