N-Heterocyclic carbene-metal complexes derived from imidazolium-linked cyclophane and biimidazolium salts

Valerie Jane Hesler

Research output: ThesisDoctoral Thesis

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This thesis presents an investigation into the synthesis of metal complexes of (Nheterocyclic carbene)-based cyclophanes. There were three main areas of focus: synthesis and complexation of bis(4,5-dihydroimidazolium) salts; the synthesis and complexation of phenol-functionalised imidazolium cyclophanes; and the synthesis and complexation of (N-heterocyclic carbene)-based cyclophanes by C-C bond activation of biimidazolium salts with electron-rich metals. The synthesis of xylyl-linked bis(4,5-dihydroimidazolium) salts was investigated. Attempts to prepare these compounds by the cyclisation of a tetraamine (linear or macrocyclic) were unsuccessful due difficulties in preparing the tetraamines. The target compounds could be prepared by adapting the methods developed for the synthesis of bis(imidazolium) salts however problems associated with purification and stability of the products prevented complexation studies. A series of phenol-, phenoxide- and anisole-functionalised imidazolium cyclophanes were prepared. Their structural properties were investigated using dynamic nmr studies and X-ray crystallography. Complexation of the functionalised cyclophanes was investigated. The phenol cyclophane I formed a dinuclear complex with mercury(II). This complex is the first example of a complex derived from a phenol-functionalised imidazolium cyclophane. However the anisole cyclophane II and the unsymmetrical phenol/ortho cyclophane III were unable to form complexes possibly due to steric hindrance and instability of the cyclophane respectively. Preliminary complexation studies of the bis(imidazolium)phenol V suggested that complexation with palladium(II) and mercury(II) were possible but more work is required to determine the optimum reaction conditions. A series of biimidazolium salts VI (both new and known) were prepared. Previously reported biimidazolium salts have very low solubility in common solvents therefore the incorporation of long alkyl chains to the bridging group was investigated as a means to improve the solubility. The structure of the salts was explored using a range of techniques including dynamic nmr spectroscopy, cyclic voltammetry, UV/Visible spectroscopy, X-ray crystallography and mass spectrometry. Some of the biimidazolium salts were able to rotate about the C2-C2' bond and the free energy of activation for this process was estimated using dynamic nmr studies. C-C bond activation of the biimidazolium salts with palladium(0) was used to form a series of palladium(II) complexes (VII) of (NHC)-based cyclophanes. These reactions are the first examples of the synthesis of bis(NHC) complexes by C-C bond activation. The reactivity of the biimidazolium salts with palladium(0) was compared to their solution structure and it was found that only the biimidazolium that were able to rotate about the C2-C2' bond could react with palladium(0).
Original languageEnglish
QualificationDoctor of Philosophy
Publication statusUnpublished - 2008


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