New methods for the synthesis of diynyl, diyndiyl and bis(diyndiyl) ruthenium (II) complexes.
| dc.contributor.advisor | Bruce, Michael Ian | en |
| dc.contributor.author | Scoleri, Nancy | en |
| dc.contributor.school | School of Chemistry and Physics : Chemistry | en |
| dc.date.issued | 2008 | en |
| dc.description.abstract | Chapter One outlines the different methods described in the literature for the synthesis of diynyl, symmetric and asymmetric diyndiyl complexes. The extension to complexes containing a central bridging group within the carbon chain is also introduced with the description of two different linking groups, either an organic or organometallic moiety. A brief overview of molecular electronics and one method of evaluation of electronic communication, cyclic voltammetry, are also addressed. Chapter Two describes the synthesis of novel symmetric and asymmetric bis(diyndiyl) ruthenium(II) complexes of general formula {LnM}-C≡CC≡C-{M”L”p}- C≡CC≡C-{M’L’m}, featuring two transition metal fragments linked by either a Ru(dppe)2 moiety or a trinuclear copper(I) or silver(I) cluster M3(μ-dppm)3 (M = Cu, Ag). Through the use of cyclic voltammetry, it was shown that the inclusion of these three particular bridging groups allows electronic communication between the two terminal end-groups. The chemistry of the starting material trans-Ru(C4H)2(dppe)2 (1) is also described, forming novel complexes when reacted with AuCl(PPh3) or TCNE. Chapter Three describes a new convenient synthetic route to diynyl and diyndiyl ruthenium(II) complexes. Lithiation of the ruthenium(II) diynyl complexes Ru(C≡CC≡CH)(dppe)Cp* and Ru(C≡CC≡CH)(PPh3)2Cp with n-BuLi yields the lithium complexes Ru(C≡CC≡CLi)(dppe)Cp* and Ru(C≡CC≡CLi)(PPh3)2Cp. The most favorable conditions for their formation are examined by using NMR spectroscopy and different assay reactions. These lithium species are further reacted with a range of metal halides to give new asymmetric diyndiyl complexes of general formula [Ru](C≡CC≡C){MLn} (where [Ru] = Ru(dppe)Cp*, Ru(PPh3)2Cp). Chapter Four investigates the reactivity of the novel lithium complex Ru(C≡CC≡CLi)(dppe)Cp* synthesised in Chapter Three. The nucleophilic nature of this complex is assessed with a range of electrophiles such as organic substrates or polyfluoroaromatic compounds. A number of new complexes are prepared and singlecrystal X-ray structure determinations are reported for many of the complexes. The electrochemistry of some of these complexes is also described. Chapter Five summarises the reactions of diynyl ruthenium(II) complexes Ru(C≡CC≡CR)(dppe)Cp* (where R = H, TMS, Au(PPh3)) with three azide reagents TMSN3, TsN3 and AuN3(PPh3). The reactions are suggested to undergo a Huisgen 1,3-alkyne-azide cycloaddition to generate 1,2,3-triazoles which further react to give the various products. The complexes synthesised are characterised by spectroscopic methods and, where possible, by X-ray structure determination. Furthermore, the reactions of the complexes Ru(C≡CC≡CH)(PPh3)2Cp and Ru(C≡CH)(dppe)Cp* with azides to give the ruthenium azido complexes [Ru]N3 (where [Ru] = Ru(PPh3)2Cp, Ru(dppe)Cp*) are described. | en |
| dc.description.dissertation | Thesis (Ph.D.) - University of Adelaide, School of Chemistry and Physics, 2008 | en |
| dc.identifier.uri | http://hdl.handle.net/2440/49426 | |
| dc.subject | diynyl; diyndiyl; rutherium; organometallic | en |
| dc.title | New methods for the synthesis of diynyl, diyndiyl and bis(diyndiyl) ruthenium (II) complexes. | en |
| dc.type | Thesis | en |