- Title
- Isocyanide complexes of rhenium
- Creator
- Schoultz, Xandri
- Subject
- Isocyanides
- Subject
- Rhenium
- Subject
- Complex compounds
- Date Issued
- 2013
- Date
- 2013
- Type
- Thesis
- Type
- Masters
- Type
- MSc
- Identifier
- vital:10360
- Identifier
- http://hdl.handle.net/10948/d1021069
- Description
- This study investigates the synthesis of rhenium(III)-isocyanide complexes with potentially bidentate ligands, as well as the reactivity of isocyanide ligands toward rhenium(I) and (V). The crystal structures of all the complexes have been determined by X-ray diffraction methods. The coordination behaviour of trans-[ReIIICl3(t-BuNC)(PPh3)2] with aniline and its derivatives were investigated. The isocyanide-containing rhenium(V) complexes [ReCl3(t-BuNC)(L)(PPh3)] were isolated, with the ligands H2L (aniline, o-phenylenediamine and anthranilic acid). In all these complexes the dianionic ligands L are coordinated monodentately as the imide. However, with 2-aminophenol the complexes [ReVCl2(t-BuNC)(L)(PPh3)2](ReO4) and [ReIIICl2(t-BuNC)(ibq)(PPh3)2] (ibq- = 2-iminobenzoquinonate) were identified as the products. [ReCl2(t-BuNC)(L)(PPh3)2](ReO4) is the product of a disproportionation reaction from Re(III) to Re(VII) and Re(V). All the above complexes show a distorted octahedral geometry around the rhenium. The products of the reaction of the Re(I) complex [Re(CO)5Cl] with isocyanides (tert-butyl- and cyclohexylisocyanide) are reported. Rhenium(I) tricarbonyl complexes of the form [Re(CO)3(CNR)2Cl] were isolated and they were characterized structurally and spectroscopically. The tricarbonyls are coordinated in the typical facial-fashion, whereas the isocyanides are coordinated cis to each other. The reaction of [Re(CO)3(t-BuNC)2Cl] with H2O led to the formation of the rhenium(I) complex [Re(CO)3(t-BuNC)2(OH2)] in which the aquo ligand can readily be substituted by a more complex ligand. The reaction of the rhenium(V) complexes cis-[ReO2I(PPh3)2] and mer-[ReOCl3(SMe2)(OPPh3)] with isocyanides were studied. The seven-coordinate trigonal prismatic, square faced monocapped rhenium(III) complex [ReI3(t-BuNC)3(PPh3)] was surprisingly isolated upon reacting cis-[ReO2I(PPh3)2] with tert-butyl isocyanide. The dimeric complex (μ-O)[ReOCl2(CNC6H11)2]2 was obtained from the reaction of mer-[ReOCl3(SMe2)(OPPh3)] with cyclohexyl isocyanide.
- Format
- vii, 109 leaves
- Format
- Publisher
- Nelson Mandela Metropolitan University
- Publisher
- Faculty of Science
- Language
- English
- Rights
- Nelson Mandela Metropolitan University
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