Synthesis of iminophosphine and phosphinoiminol cyclometallated Pt (II) and Pt (IV) chloro complexes and studies into their biological and photophysical properties

This thesis focuses on the synthesis and analysis of novel chloride based platinum complexes derived from iminophosphine and phosphinoamide ligands, along with studies on their reactivity towards substitution and oxidation reactions. Also explored here are the potential applications of these complexes for biological and luminescent purposes. Chapter one provides an extensive overview of platinum coordination chemistry with examples of various mixed donor ligands along with the history of platinum anticancer therapy. It also looks at metals in medicine, both for biological functions as well as for therapeutic purposes and gives a background to some other applications for platinum complexes. Chapter two outlines the design and synthetic strategies employed for the development of novel platinum (II) chloride complexes from iminophosphine and phosphinoamide ligands. Also reported is the cyclometallation of these complexes to form stable tridentate mixed donor platinum (II) compounds. In Chapter three the development of a direct method for displacing a chloride from a platinum metal centre with a desired phosphine is reported. Numerous methods for successful oxidation of the platinum (II) complexes will also be explored, leading to novel platinum (IV) complexes being reported here also. The importance of stabilisation of the displaced anion, chloride, by the solvent system will also be discussed in this chapter. Chapter four investigates the reactivity of the platinum (II) complexes towards two different biomolecules to form novel platinum bio-adducts. The potential application of the platinum (II) cyclometallates as chemotherapeutics will also be explored here using in-vitro cancer cell testing. Finally, luminescence studies are also reported here for the ligands and platinum complexes reported in chapter two and three to investigate potential applications in this field also. Chapter five provides a final conclusion and an overall summary of the entire project as well as identifying key areas for future work.

Predictions of the Pt(8)Ti phase in unexpected systems.

The binary A(8)B phase (prototype Pt(8)Ti) has been experimentally observed in 11 systems. A high-throughput search over all the binary transition intermetallics, however, reveals 59 occurrences of the A(8)B phase: Au(8)Zn(dagger), Cd(8)Sc(dagger), Cu(8)Ni(dagger), Cu(8)Zn(dagger), Hg(8)La, Ir(8)Os(dagger), Ir(8)Re, Ir(8)Ru(dagger), Ir(8)Tc, Ir(8)W(dagger), Nb(8)Os(dagger), Nb(8)Rh(dagger), Nb(8)Ru(dagger), Nb(8)Ta(dagger), Ni(8)Fe, Ni(8)Mo(dagger)*, Ni(8)Nb(dagger)*, Ni(8)Ta*, Ni(8)V*, Ni(8)W, Pd(8)Al(dagger), Pd(8)Fe, Pd(8)Hf, Pd(8)Mn, Pd(8)Mo*, Pd(8)Nb, Pd(8)Sc, Pd(8)Ta, Pd(8)Ti, Pd(8)V*, Pd(8)W*, Pd(8)Zn, Pd(8)Zr, Pt(8)Al(dagger), Pt(8)Cr*, Pt(8)Hf, Pt(8)Mn, Pt(8)Mo, Pt(8)Nb, Pt(8)Rh(dagger), Pt(8)Sc, Pt(8)Ta, Pt(8)Ti*, Pt(8)V*, Pt(8)W, Pt(8)Zr*, Rh(8)Mo, Rh(8)W, Ta(8)Pd, Ta(8)Pt, Ta(8)Rh, V(8)Cr(dagger), V(8)Fe(dagger), V(8)Ir(dagger), V(8)Ni(dagger), V(8)Pd, V(8)Pt, V(8)Rh, and V(8)Ru(dagger) ((dagger) = metastable, * = experimentally observed). This is surprising for the wealth of new occurrences that are predicted, especially in well-characterized systems (e.g., Cu-Zn). By verifying all experimental results while offering additional predictions, our study serves as a striking demonstration of the power of the high-throughput approach. The practicality of the method is demonstrated in the Rh-W system. A cluster-expansion-based Monte Carlo model reveals a relatively high order-disorder transition temperature.

Contractual termination of leases: lessons from the Commonwealth: Pt. 1

This, the first part of a three-part article on contractual termination of leases, considers the extent to which determination of a lease in accordance with the contract law principles of frustration and acceptance of a repudiatory breach has been accepted by Commonwealth courts. Reviews the approaches adopted by the courts in Canada, the US and Australia to the application of contractual principles to landlord and tenant disputes.

Contractual termination of leases: lessons from the Commonwealth: Pt. 2

This, the second part of a three-part article on contractual termination of leases, considers the extent to which English courts have allowed the contract law principles of frustration and acceptance of a repudiatory breach to be applied to leaseholds. Distinguishes cases involving a repudiatory breach by a landlord from those where the tenant is the one in breach.

Contractual termination of leases: lessons from the Commonwealth: Pt. 3

This, the third part of a three-part article on the contractual termination of leases, examines, with reference to UK and Commonwealth case law, the connection between contractual termination and the provisions of legislation including the the Landlord and Tenant Act 1954 Pt II relating to forfeiture and termination of business tenancies. Considers why contractual termination by acceptance of a repudiatory breach is a necessary development to protect tenants in the event of a landlord's significant default.

Magnetic and structural properties of Co films deposited onto obliquely sputtered Pt underlayers

Co films deposited on obliquely sputtered Pt underlayers of 100 Angstrom or greater have produced coercivities in excess of 800 Oe, and anisotropy fields over 950 Oe. The coercivity and anisotropy field increase with Pt deposition angle and thickness. A Pt capping layer has a detrimental effect on properties but a Cu capping layer does not. Films with an obliquely deposited underlayer exhibit reduced density and increased interface roughness compared to normally deposited films. Normally deposited Pt underlayers display a (111) texture, while those deposited obliquely show an increasingly random texture with Pt thickness and deposition angle. The trilayers fabricated in this study are presented as candidates for use in giant magnetoresistance sensors. (C) 2002 American Institute of Physics.

Non-linear electronic transport in Pt nanowires deposited by focused ion beam

Electrical transport and structural properties of platinum nanowires, deposited using the focussed ion beam method have been investigated. Energy dispersive X-ray spectroscopy reveals metal-rich grains (atomic composition 31% Pt and 50% Ga) in a largely non-metallic matrix of C, O and Si. Resistivity measurements (15-300 K) reveal a negative temperature coefficient with the room-temperature resistivity 80-300 times higher than that of bulk Pt. Temperature dependent current-voltage characteristics exhibit non-linear behaviour in the entire range investigated. The conductance spectra indicate increasing non-linearity with decreasing temperature, reaching 4% at 15 K. The observed electrical behaviour is explained in terms of a model for inter-grain tunnelling in disordered media, a mechanism that is consistent with the strongly disordered nature of the nanowires observed in the structure and composition analysis.

An investigation of possible mechanisms of the water-gas shift reaction over a ZrO2-supported Pt catalyst

The present work investigates the reactivity of the surface species observable by in situ DRIFTS formed over a Pt/ZrO2 during the water-gas shift (WGS) reaction. A DRIFTS cell/mass spectrometer system was operated at the chemical steady state during isotopic transients to yield information about the true nature (i.e., main reaction intermediate or spectators) of adsorbates. Only carbonyl and formate species were observed by DRIFTS under reaction conditions; the surface coverage of carbonate species was negligible. Isotopic transient kinetic analyses revealed that formates exchanged uniformly according to a first-order law, suggesting that most formates observed by DRIFTS were of the same reactivity. In addition, the time scale of the exchange of the reaction product CO2 was significantly shorter than that of the surface formates. Therefore, a formate route based on the formates as detected by DRIFTS can be ruled out as the main reaction pathway in the present case. The number of precursors of the reaction product CO2 was smaller than the number of surface Pt atoms, suggesting that carbonyl species or some \