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Synthesis and coordination chemistry of entangled ligands derived from a pybox-based macrocycle
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Parker, Gemma Louise (2020) Synthesis and coordination chemistry of entangled ligands derived from a pybox-based macrocycle. PhD thesis, University of Warwick.
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Official URL: http://webcat.warwick.ac.uk/record=b3520390
Abstract
Rigid tridentate pincer ligands are frequently used in organometallic chemistry and catalysis, conferring thermal stability and supporting a wide range of metal-based reactivity. Studying the coordination chemistry of alkanes is a formidable challenge in synthetic inorganic chemistry, but systems supported by pincer ligands have shown considerable promise. For instance, use of a rhodium(I) PONOP complex has enabled the synthesis and characterisation of a σ-methane derivative at low temperature. Seeking to circumvent difficulties associated with dissociation of the hydrocarbon substrate, macrocyclic rhodium systems featuring a mechanically interlocked alkyl chain are proposed to facilitate investigation of intermolecular M∙∙∙H–C bonding interactions.
The synthesis and coordination chemistry of the pybox-based [2]rotaxane Rpybox is herein described. This novel ligand was prepared following optimisation of a reported active metal template procedure, where the interlocked architecture is captured using a nickel-catalysed C(sp3)–C(sp3) homocoupling reaction. Rhodium(I/III), iridium(III) and ruthenium(II) complexes of Rpybox have been investigated, supplemented by explorative work using the macrocyclic component (Mpybox) and an acyclic variant (Phpybox). Low coordinate cationic rhodium complexes of Rpybox could be generated using halide abstraction reactions and the presence of M∙∙∙H–C interactions was probed using spectroscopic techniques.
Item Type: | Thesis (PhD) | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Library of Congress Subject Headings (LCSH): | Macrocyclic compounds, Ligands, Ligands -- Synthesis, Rhodium compounds, Coordination compounds | ||||
Official Date: | November 2020 | ||||
Dates: |
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Institution: | University of Warwick | ||||
Theses Department: | Department of Chemistry | ||||
Thesis Type: | PhD | ||||
Publication Status: | Unpublished | ||||
Supervisor(s)/Advisor: | Chaplin, Adrian | ||||
Format of File: | |||||
Extent: | viii, 185 leaves : illustrations | ||||
Language: | eng |
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