Thesis (Ph. D.)--University of Texas at Austin, 2007. / Vita. Includes bibliographical references.

Thesis (Ph. D.)--University of Washington, 2006. / Vita. Includes bibliographical references (leaves 74-83).

Thesis (Ph. D.)--University of Washington, 2000. / Vita. Includes bibliographical references (leaves 170-184).

Th. 3e cycle--Chim. struct.--Besançon, 1982. N°: 402.

The thesis is presented in two parts, part one concerns the synthesis and biodistribution of technetium–porphyrin complexes. A series of compounds with the general formula TcO(Porhyrin)OAc and TcO(Phthalocyanine)OPh have been synthesised via a novel route. The starting material comprised NH4TcO4 with acetic acid for the porphyrin and phenol for the phthalocyanine. The compounds have been characterised both qualitatively and quantitatively by infra-red, ultra-violet and mass spectrometry. Thin Layer Chromatography (TLC) and electrophoresis have also been employed to further analyse the complexes. Preliminary biodistribution studies have been performed in a model of inflamed tissue. The results suggest that the labelled porphyrins are capable of imaging such tissue. One of the complexes was tested for an ability to accumulate in, and image tumours, however this proved unsuccessful.

No description available.

Thorium(IV) and uranium(IV) coordination complexes have been studied for the last 60 years. They have shown interesting reactivity that is often divergent from that of transition metal complexes, and that also provides an insight into some unanticipated differences between thorium(IV) and uranium(IV). An introduction to thorium(IV) and uranium(IV) organometallic chemistry supported by carbocyclic and N-donor ligands is given in Chapter One. The reactivity of actinide alkyl, amide and alkynyl complexes towards small molecules is discussed and select examples provided. The redox chemistry of thorium and uranium is also introduced. Chapter Two describes the alkylation and amination chemistry of uranium(IV) and thorium(IV) trans-calix[2]benzene[2]pyrrolide ((L)2-) complexes, [(L)AnCl2], yielding new actinide(IV) complexes of the type [M(L-2H)An(R)] (M = Li or K, R = Me, CH2SiMe3, CH2Ph, N(SiMe3)2), where (L)2- undergoes further deprotonation to (L-2H)4-. Additionally, the lability of the [M(L-2H)An(R)] “ate”-complexes towards M+ ion exchange is addressed. Further, the selective ligand reprotonation of (L-2H)4- to (L)2- using HSiR'3 (R' = Me, iPr) and [Et3NH][BPh4] yielding [(L)An(C≡CSiR'3)2] and [(L)An(R)][BPh4] respectively, is explained. The reactivity of these complexes towards amines, silanes, alkenes, tin hydrides, silicone grease, tBuNC, H2, CO, CO2 or CS2 is described. Crystallographic characterisation shows that [(L)Th(N(SiMe3)2)][BPh4] contains an unusual example of a thorium(IV) bis-arene coordination mode. The reactivity of [(L)Th(C≡CSiMe3)2] towards a number of substrates including alkenes, [Ni(COD)2], [Pt(norbornene)3], P4, CO2 or H2 is also discussed. Activation of CO2 by [(L)Th(C≡CSiMe3)2] at 80 °C results in (L)2- functionalisation and abstraction to yield a new tricyclic organic molecule with the general formula LCO. The addition of [Ni(COD)2] to [(L)Th(C≡CSiMe3)2] and PR''3 (R'' = phenyl, cyclohexyl) yields heterobimetallic complexes [(L)Th(C≡CSiMe3)2·Ni(PR''3)]; these products display both dipyrrolic and bis-arene coordination. The changes in ligand coordination mode are discussed alongside DFT computational analyses that have been carried out by collaborators. The substitution reactions of [(L)AnCl2] with NaBH4 to form actinide(IV) borohydride complexes [(L)An(BH4)2] and subsequent attempted abstractions of BH3 from [(L)Th(BH4)2] are presented. Conclusions are provided at the end of the chapter. Chapter Three focusses on the oxidation chemistry of uranium(IV) within the (L)2- and (L-2H)4- ligand framework, prompted by the isolation of a uranium(V) complex [Li[(L)UO2]·LiI] from the oxidation of the uranium(IV) complex [Li(L-2H)U(Me)]. Conclusions are provided at the end of the chapter. Experimental methods and characterising data are given in Chapter Four.

The infrared spectra of mixtures of HC1 and the following have been recorded in the gas phase and low temperature matrices: argon, ethene, ethyne, de-benzene, fluorobenzene, CO, CO 2 , SOz, CC1*, CHCls, de-acetone, ethanal, HCN and acrylonitrile. The features which have been measured are: firstly the changes in the integrated intensity of lines in the rotation-vibration spectrum of the fundamental HC1 band as a function of interactions with other components of the mixture, and secondly bands associated with specific interactions forming hydrogen-bonded complexes. The enhancement of HC1 is generally found to vary linearly with the pressure of added gas over a limited pressure range. Assuming that line enhancement is caused by collisionally-induced rotation-translation energy exchange to or from the HC1 molecule, a combination of expressions derived from Ehrenfest's Adiabatic Principle and the "rigid rotor" approximation leads to a model which qualitatively predicts the enhancements observed. The model also rationalises the enhancement of HCN and SOa absorptions by HC1. Examination of the experimentally determined data leads to the conclusion that the total intermolecular force between the monomer base and HC1 controls the degree of enhancement but it is concluded that there is no general connection between the degree of HC1 enhancement and hydrogen-bond strength. Hydrogen-bonded complexes were examined in the gas and argon matrix phases and the shifts in the modified hydrogen chloride stretch compared for various bases. The spectra of pi-complexes formed between HC1 and ethene, ethyne and benzene were found to be detectable by low-resolution infrared spectroscopy at room temperature. Complexation of HCN, he-acetone and de-acetone with HC1 caused CN and C=O band shifts. The Chem-X molecular modelling program was evaluated by using it to predict the geometry of simple complexes for which experimental data is already available. It is concluded that the program requires more development before it can be confidently used as a theoretical aid with which to study hydrogen-bonded dimers.

No description available.

A series of bis [e] and [a] fused dibenzannulenes/cyclophanes have been synthesized for the first time using benzyne-like intermediates (annulynes). These include the dibenzannulene trans-2,9-di-t-butyl-14c, 14d-dihydro-14c-14d-dimethyldibenzo[fg,op]naphthacene 82b, and the metacyclophanedienes anti-[1,2;9,10]- dibenzo-5, 13-di-t-butyl-8,16-dimethyl[2.2]metacyclophane 82a, and anti-[1,2-b; 9,10-b]- dinaphtho-5,13-di-t-butyl-8,16-dimethyl[2.2]metacyclophane 85a. From these compounds several metal complexes including trans-{μ- [( 1,2,3,4,4a, 14b-η:8a,9,10,11,12,12a-η)-12c, 12d-dihydro-12c-12d-dimethylbenzo[ rst]pentaphene]]hexacarbonyldichromium 100, have been synthesized. Among the bis [e] fused compounds, pairs 82a/82b and 95a/95b show reversible and repeatable photo-switching properties both in solution and in the solid state. The pyrene forms 82b and 95b are characterized at low temperature and they thermally return to their cyclophane forms 82a and 95a at room temperature. A polystyrene based film of 82 shows a much better bistability required for photo-switching units. These properties make them potential candidates for optical memory units. For the similar naphtho[e] fused compound 95a, no pyrene isomer 95b was detected upon irradiation with UV light. Based on the NMR data, relative bond fixing abilities (RBFA) of several species are measured. The order is: [special characters omitted] > Benzene > Oxanorbomadiene > lU Norbomadiene The reduced species, oxanorbomene and norbomene, do not induce any significant bond localization on the [14] annulene ring. / Graduate