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Spectroscopic Studies Of Metal Binding To Metallothioneins, Annie Yiu-Chu Law
Spectroscopic Studies Of Metal Binding To Metallothioneins, Annie Yiu-Chu Law
Digitized Theses
Metallothioneins (MT) are a class of cysteine-rich proteins that bind a wide variety of metal ions. Although it has been suggested that the structure of the metal binding sites in Cd,Zn-MT involves two metal clusters (alpha and beta) which coordinate the metals through a tetrahedral arrangement of cysteine residues, considerably less information is available concerning the metal binding sites in MT containing Hg('2+) and Cu('+). In this work, absorption, circular dichroism and magnetic circular dichroism spectroscopies have been used to characterize metal binding to metallothioneins. Three species of MT (rat, guinea pig and crab) have been studied. In addition to …
Mechanisms Of Thermal And Photochemical Reactions Of Organoplatinum Complexes, Ross Henry Hill
Mechanisms Of Thermal And Photochemical Reactions Of Organoplatinum Complexes, Ross Henry Hill
Digitized Theses
This thesis describes investigations into a variety of thermal and photochemical reactions of organoplatinum complexes.;The mechanism and energetics of the reaction of tertiary phosphine ligands, L, with {lcub}Pt(,2)H(,n)Me(,3-n)((mu)-dppm)(,2){rcub}('+), (n = 2,1) (dppm = bis(diphenylphosphino)methane), have been determined. The reaction was found to occur through coordination of L followed by reductive elimination. In each case H(,2) was found to be eliminated and the platinum(I) products formed were {lcub}Pt(,2)HL((mu)-dppm)(,2){rcub}('+) and {lcub}Pt(,2)MeL((mu)-dppm)(,2){rcub}('+). The rate constants and equilibrium constants were determined at a variety of temperatures, allowing construction of a reaction coordinate energy level diagram.;The photochemically induced reductive elimination reactions of the complexes {lcub}Pt(,2)H(,3-n)Me(,n)((mu)-dppm)(,2){rcub}('+), …
The Coordination Chemistry Of Fluorinated-Alcohol Thioethers, Rene Theodoor Boere
The Coordination Chemistry Of Fluorinated-Alcohol Thioethers, Rene Theodoor Boere
Digitized Theses
The synthesis of fluorinated-alcohol thioethers of the type HOC(CF(,3))(,2)CH(,2)SR (R=Me,Ph,('t)Bu), is described. These can be deprotonated to give bidentate, uninegative hybrid ligands, denoted L('-), which contain both a hard (alkoxide) and a soft (thioether) donor site (HSAB theory). They favour complex-formation with soft, over hard metal ions: CuL(,2) (R=Me) is the only stable first- row transition metal complex accessible; PdL(,2) and PtL(,2) (R=Me,Ph,('t)Bu) are all stable. By NMR, PtL(,2) is cis, with syn and anti forms from pyramidal sulfur; PdL(,2) is a cis/trans mixture of syn- and anti-isomers. Mixed-ligand complexes of the type {lcub}ML(Cl)PPh(,3){rcub} and {lcub}ML(PR(,3))(,2){rcub}BF(,4) were also prepared, M …
Oxidative Addition To Platinum(Ii) Complexes, Patrick Kevin Monaghan
Oxidative Addition To Platinum(Ii) Complexes, Patrick Kevin Monaghan
Digitized Theses
This thesis describes the oxidative addition of alcohols, water and organic halides to dimethyl(2,2-bipyridine)platinum(II) (complex (I)) and to dimethyl(1,10-phenanthroline)platinum(II) (complex (II)). The work has involved characterising the reaction products and investigating the mechanism of oxidative addition. Up to now very little mechanistic work has been done for oxidative addition at platinum(II) centres.;Complexes (I) and (II) react with methanol, ethanol and isopropanol to produce the first series of platinum(IV) alkoxides of general formula {lcub}PtMe(,2)(OR)(N N)H(,2)O{rcub}('+){lcub}OH{rcub}('-) (N N = bipy or phen; R = Me, Et, ('i)Pr). Characterisation was achieved by ('1)H nmr, ('13)C nmr and elemental analysis. In an analogous reaction …
Metallacyclobutane Chemistry, John Thomas Burton
Metallacyclobutane Chemistry, John Thomas Burton
Digitized Theses
This thesis describes the preparation, characterisation, and reactivity of a new class of platinacyclobutane complexes, containing a hydroxyl or ester functionality. The monomeric compounds are prepared by the reaction of Zeise's dimer with the appropriate cyclopropane derivative and subsequent addition of pyridine.;Owing to the presence of the hydroxyl group, these complexes have been shown to interact with the shift reagent, Eu(fod)(,3), so as to greatly simplify their ('1)H-N.M.R. spectra. Using the results obtained from this study and the equation of Karplus, comparisons are drawn between ring conformations in the solid state and solution which indicate significant puckering of these complexes …