No description available.

The reactivity of copper chloride (CuC1[subscript x], 1 < x < 2) towards chlorine and its catalytic activity in the chlorination of propane have been studied. The oxidation of copper (I) chloride by chlorine was found to be diffusion controlled after the first 25% of reaction. For the chlorination of propane, CuC1 was catalytically inactive, CuC1₂ was active, but the maximum activity was found in the range CuC1₁․₅ to CuC1₁․₈ with two peaks at roughly CuC1₁․₅₇ and CuC1₁․₇₈. Both reactions appear to have an active centre in common — a Cu⁺ ion which is capable of accepting a proton. The phase of maximum catalytic activity is a highly defective CuC1₂ phase containing such centres. The mechanism for the catalytic chlorination involves the homolytic splitting of C₃H₈ and stabilization of surface radicals through proton transfer into the bulk. No compound other than CuC1 and CuC1₂ was found in the CuC1x system by X-ray powder studies. However, the results of X-ray powder, electrical conductivity and magnetic susceptibility studies provide convincing evidence for the existence of a defective CuC1₂ phase with interstitial cations as well as a cation-deficient CuC1 phase in CuC1x. Furthermore, these results are consistent with a structural change at x ∼1.63 as suggested also by the kinetic studies. While the present work shows many interesting features of the CuC1x system, there is plenty of room for further exploration in this hitherto virtually unknown field. Suggestions for future work related to the present findings are outlined in this thesis. / Science, Faculty of / Chemistry, Department of / Graduate

Magnetic susceptibility studies over the temperature range 87-330°K, on sixteen complexes of copper (11) are reported. The compounds are conveniently divided into two groups. Group I compounds (copper (11) benzoate and its monopyridine adduct, copper (11) meta-chlorobenzoate and its monopyridine and mono-p-dioxane adducts and the monopyridine and hemipyridine adducts of copper (11) para-chlorobenzoate ) possess magnetic properties expected for a binuclear system and values of the exchange integrals have been calculated, for these compounds. The group 11 compounds (the dipyrldlne adducts and the basic salts of copper (ll) benzoate, copper (11) ortho-, meta- and para-chlorobenzoate ) exhibit only weak magnetic interaction --- their magnetic susceptibilities obeying the Curie-Weiss law with small Weiss constants --- and they are considered to have polymeric structures. Copper (11) para-chlorobenzoate exhibits properties intermediate between the group I and 11 compounds. Confirmatory evidence for assigning binuclear structures to the group I compounds has been obtained from the presence, in the spectra of the group I compounds, of a band at about 400 mμ which is absent from the spectra of the group 11 compounds. Infrared spectra are reported for all the compounds studied and a partial assignment has been made. / Science, Faculty of / Chemistry, Department of / Graduate

The reaction of a number of (trialkylstannyl)copper reagents with 2-alkynoates, N,N-dimethyl-2-alkynaraides and 1-alkynes is described. It has been found that the (trimethylstannyl)copper reagents 14 and 43-46 efficiently transfer the trimethylstannyl group to oc-alkynoates. Reagent 14 (THF, -48°C) provided predominantly the (Z)-3-trimethyl-stannyl-2-alkenoate (22), reagents 44 and 45 (THF, -48°C) afforded essentially exclusively the corresponding (E) isomer 21, while reagents 43 and 46 gave a mixture of isomers. Using the above methodology, ethyl 2-pentynoate was converted into either (Z)- or (E)-3-( tri-n-butylstannyl)-2-pentenoate. The (E) isomer was converted into the vinylstannane 188 which was transformed (MeLi, THF, -20°C) into the corresponding stereochemically homogeneous vinyllithium reagent and elaborated into the acyl portion of (±)-triophamine (172), a diacylguanidine recently isolated from Triopha catalinae. Reaction of 2-alkynoates with excess 44 or 45 (THF, 0°C) afforded, as essentially the only products, (E)-2,3-bis(trimethyl-stannyl)-2-alkenoates (115). One member of this new class of compounds, ester 114 (=115, R = Me, R' = Et) was selectively transmetalated (MeLi, THF, -98°C) and the resultant nucleophilic species was allowed to react with a number of reactive electrophiles to produce esters of general structure 141. / Science, Faculty of / Chemistry, Department of / Graduate

No description available.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Master / Master of Philosophy

No description available.

ii, 137 leaves : ill., graphs, tables ; 31 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1980

Thesis (Ph.D.) -- University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1980.