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Coordination chemistry of a calix[4]arene-based NHC ligand : dinuclear complexes and comparison to IiPr2Me2
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Patchett, Ruth and Chaplin, Adrian B. (2016) Coordination chemistry of a calix[4]arene-based NHC ligand : dinuclear complexes and comparison to IiPr2Me2. Dalton Transactions, 45 (21). pp. 8945-8955. doi:10.1039/c6dt01001f ISSN 1477-9226.
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Official URL: http://dx.doi.org/10.1039/C6DT01001F
Abstract
The preparation and coordination chemistry of 5,17-bis(3-methyl-1-imidazol-2-ylidene)-25,26,27,28-tetrapropoxycalix[4]arene (1) is described. Starting from the bis(imidazolium) pro-ligand 1·2HI, the free carbene 1 was readily generated in solution through deprotonation using K[OtBu] and its reactivity with rhodium(I) dimers [Rh(COD)Cl]2 (COD = 1,5-cyclooctadiene) and [Rh(CO)2Cl]2 investigated. Dinuclear complexes were isolated in both cases, where the calix[4]arene-based NHC ligand adopts a bridging μ2-coordination mode, and in one case characterised in the solid-state by X-ray diffraction. Using instead an isolated and well-defined (mononuclear) silver transfer agent, generated by reaction of 1·2HI with Ag2O in the presence of a halide extractor, reactions with [Rh(COD)Cl]2 and [Rh(CO)2Cl]2 produced cationic dinuclear complexes bearing μ2-1 and μ2-Cl bridging ligands. The structural formulation of the novel dinuclear adducts of 1 was aided through spectroscopic congruence with model complexes, containing monodentate 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (IiPr2Me2).
Item Type: | Journal Article | ||||||||
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Subjects: | Q Science > QD Chemistry | ||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||||
Library of Congress Subject Headings (LCSH): | Organometallic chemistry, Catalysis, Ligands | ||||||||
Journal or Publication Title: | Dalton Transactions | ||||||||
Publisher: | Royal Society of Chemistry | ||||||||
ISSN: | 1477-9226 | ||||||||
Official Date: | 10 May 2016 | ||||||||
Dates: |
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Volume: | 45 | ||||||||
Number: | 21 | ||||||||
Page Range: | pp. 8945-8955 | ||||||||
DOI: | 10.1039/c6dt01001f | ||||||||
Status: | Peer Reviewed | ||||||||
Publication Status: | Published | ||||||||
Access rights to Published version: | Open Access (Creative Commons) | ||||||||
Date of first compliant deposit: | 11 July 2016 | ||||||||
Date of first compliant Open Access: | 11 July 2016 | ||||||||
Funder: | Royal Society (Great Britain), Engineering and Physical Sciences Research Council (EPSRC), University of Warwick, Advantage West Midlands (AWM), European Regional Development Fund (ERDF) |
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