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Synthesis and coordination chemistry of complexes of chelating phosphine-carbene ligands

Al-Saadi, Sultan 2015. Synthesis and coordination chemistry of complexes of chelating phosphine-carbene ligands. PhD Thesis, Cardiff University.
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Abstract

Results presented and discussed in this thesis are collected into 4 chapters. Chapter 1 is an introduction to the synthesis and properties of phosphine and N-heterocyclic carbine compounds and complexes. Related complexes of N-heterocyclic carbine-phosphine ligands are also reviewed in this chapter. The synthesis and characterisation of a new phosphine-functionalized N-heterocyclic carbine ligand precursor, 2.5, is described in chapter 2. A synthetic route has been successfully established for this ligand which is designed with N-methyl group on one side of the imidazole core and a pendant PR2 moiety on the other side, (where R = Pri). The ring between the phosphorus group and the imidazolium ring is bound directly to give the rigidity to the whole chelating ligand structure. The corresponding phosphine-NHC ligand was generated in situ and reacted with suitable metal precursors. In addition, the reactivity of the ligand under various conditions was shown to cause cleavage of THF with concomitant formation of an alcohol group attached to the carbene's carbon atom, 2.7. Chapter 3 describes reactions with metal precursors in the presence of a base (via free carbine) or via silver transfer agents and afforded a number of new metal complexes of the phosphine-NHC ligand. These included complexes of groups 11, 10, 9 and 7: Au (3.1), Ag (3.2), Cu (3.3), Ni (3.4), Pd (3.5), Pt (3.6), Mn (3.7) and Ir (3.8). The synthesis of Ag(I) complex was achieved by the reaction of the ligand, phosphine-imidazolium salt (2.5) with Ag2O. The synthesized phosphine N-heterocyclic carbine complexes were characterised by analytical and spectroscopic methods and in some cases by X-ray crystallography. Chapter 4 lists other attempted complexations which did not succeed to yield desired products.

Item Type: Thesis (PhD)
Status: Unpublished
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Date of First Compliant Deposit: 27 April 2016
Last Modified: 21 Oct 2016 05:37
URI: http://orca.cardiff.ac.uk/id/eprint/90079

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