title: Reactions of cyclomanganated compounds

authors: Mace, Wade

abstract: This thesis describes novel reactions of cyclomanganated compounds of the general form shown below. The ligand is bonded by a metal-carbon σ-bond, with X acting as a donor atom to form the chelate ring. The organic ligands were derived from aryl and heteroaryl ketones, chalcones, dienones and azabutadienes. 
A preliminary investigation has previously been undertaken into the reaction of carbon disulfide with some orthomanganated aryl ketones. In the present study these reactions were further investigated, with the isolation of new η2-S, S-dithiocarboxylate complexes, e.g. 46. In other cases the reaction of carbon disulfide with cyclomanganated compounds afforded the novel Mn4 species 50 in low yield. 
The reactions of orthomanganated acetyl-aryl compounds with organic isocyanides (C≡NR) afforded a number of novel compounds. For example η2-(2-acetylphenyl)-tetracarbonylmanganese (79) afforded four different types of products depending on the isocyanide; tert-butyl isocyanide produced 82, ethyl isocyanide produced 95 and 96, and 4-methoxyphenyl isocyanide produced 98 and 99. 
With orthomanganated 2-acetylthiophene, CNBut gave the quinone species 88 and 89,which showed high anti fungal and antitumor activity. 
Cyclomanganated dienones (e.g. 127) were previously known to react with alkynes to give either (η5-pyranyl)Mn(CO)3 (e.g. 130) or (η5-oxocycloheptadienyl)Mn(C0)3 (e.g.129) products. The factors influencing which product is formed were more systematically investigated and a deuterium-labelling experiment was used to probe the1,2-phenyl shift that occurs for the (η5-oxocycloheptadienyl)Mn(C0)3 products . 
A preliminary investigation of the reactions of 4-phenyl-1-(4-tolyl)-l-azabuta-1, 3-diene(TAD) with PhCH2Mn(CO)5 and unsaturated substrates including phenyl acetylene, methyl acrylate, PhNCO, ButNC and carbon disulfide is also described. A number of novel compounds were produced, including 169 from the reaction involving PhNCO. 
In contrast η2-(5-methoxy-2-acetylphenyl)tetracarbonylmanganese with ally1 isothiocyanate gave simply 2-allyl-4-methoxyacetophenone by allylation of the orthomanganated starting compound. Allyl bromide behaved similarly. However, allyl bromide and ethyl bromide when reacted with the cyclomanganated chalcone 54 gave furanone products (e.g. 190 and 191). An oxidative addition and reductive elimination mechanism was proposed to explain this reaction. 
Among others, the crystal structures of 50, 89 and 130 were determined.

text: Reactions of cyclomanganated compounds This thesis describes novel reactions of cyclomanganated compounds of the general form shown below. The ligand is bonded by a metal-carbon σ-bond, with X acting as a donor atom to form the chelate ring. The organic ligands were derived from aryl and heteroaryl ketones, chalcones, dienones and azabutadienes. 
A preliminary investigation has previously been undertaken into the reaction of carbon disulfide with some orthomanganated aryl ketones. In the present study these reactions were further investigated, with the isolation of new η2-S, S-dithiocarboxylate complexes, e.g. 46. In other cases the reaction of carbon disulfide with cyclomanganated compounds afforded the novel Mn4 species 50 in low yield. 
The reactions of orthomanganated acetyl-aryl compounds with organic isocyanides (C≡NR) afforded a number of novel compounds. For example η2-(2-acetylphenyl)-tetracarbonylmanganese (79) afforded four different types of products depending on the isocyanide; tert-butyl isocyanide produced 82, ethyl isocyanide produced 95 and 96, and 4-methoxyphenyl isocyanide produced 98 and 99. 
With orthomanganated 2-acetylthiophene, CNBut gave the quinone species 88 and 89,which showed high anti fungal and antitumor activity. 
Cyclomanganated dienones (e.g. 127) were previously known to react with alkynes to give either (η5-pyranyl)Mn(CO)3 (e.g. 130) or (η5-oxocycloheptadienyl)Mn(C0)3 (e.g.129) products. The factors influencing which product is formed were more systematically investigated and a deuterium-labelling experiment was used to probe the1,2-phenyl shift that occurs for the (η5-oxocycloheptadienyl)Mn(C0)3 products . 
A preliminary investigation of the reactions of 4-phenyl-1-(4-tolyl)-l-azabuta-1, 3-diene(TAD) with PhCH2Mn(CO)5 and unsaturated substrates including phenyl acetylene, methyl acrylate, PhNCO, ButNC and carbon disulfide is also described. A number of novel compounds were produced, including 169 from the reaction involving PhNCO. 
In contrast η2-(5-methoxy-2-acetylphenyl)tetracarbonylmanganese with ally1 isothiocyanate gave simply 2-allyl-4-methoxyacetophenone by allylation of the orthomanganated starting compound. Allyl bromide behaved similarly. However, allyl bromide and ethyl bromide when reacted with the cyclomanganated chalcone 54 gave furanone products (e.g. 190 and 191). An oxidative addition and reductive elimination mechanism was proposed to explain this reaction. 
Among others, the crystal structures of 50, 89 and 130 were determined.

year: 2003

title: A comparison of free access, multiple stimulus without replacement, and concurrent schedule preference assessment methods for evaluating food preference

authors: Bates, Nicole

abstract: Outcomes from three preference assessment methods were examined in a study of food preference with goats. The methods used were: free access, multiple stimulus without replacement, and a concurrent schedule analysis. Results from each method were compared, in terms of the preference ranking they produced. Two male goats, one domesticated wild goat and one Saanen, were used as subjects in this study. Each method yielded similar results, although the concurrent schedule test provided more comprehensive information than either of the other methods. There was moderate agreement between the multiple stimulus without replacement and the concurrent schedule tests, however the free access procedure identified only the two most highly preferred items and provided limited information on preference level of the remaining food items. Five foods were tested in this experiment, all of different texture and composition – crushed maize, sheep and goat pellets, chopped lucerne, lucerne haylage, and timothy and lucerne haylage. During the free access, goats were given unrestricted access to a particular food for 12 seconds. During the multiple stimulus without replacement, goats were presented with all five foods simultaneously and allowed to make one choice. Once the subject had selected a food by pressing the respective cover with their muzzle, that cover was removed to allow access to that food only. When the subject stopped eating, the cover was replaced - subjects could then select another food. This process was repeated until either all five feeds had been sampled or goats had not made contact with any covers for fifteen seconds. The concurrent schedule test involved making two foods available concurrently. Food delivery was determined by a VI 60s schedule and controlled by a computer software program that was linked to the apparatus. The assessment procedure was arranged so that each food was tested alongside every other food. Data was analysed in terms of the proportion of time and responses allocated to each food. Proportion of time and responses varied considerably depending on the food that was available concurrently.

text: A comparison of free access, multiple stimulus without replacement, and concurrent schedule preference assessment methods for evaluating food preference Outcomes from three preference assessment methods were examined in a study of food preference with goats. The methods used were: free access, multiple stimulus without replacement, and a concurrent schedule analysis. Results from each method were compared, in terms of the preference ranking they produced. Two male goats, one domesticated wild goat and one Saanen, were used as subjects in this study. Each method yielded similar results, although the concurrent schedule test provided more comprehensive information than either of the other methods. There was moderate agreement between the multiple stimulus without replacement and the concurrent schedule tests, however the free access procedure identified only the two most highly preferred items and provided limited information on preference level of the remaining food items. Five foods were tested in this experiment, all of different texture and composition – crushed maize, sheep and goat pellets, chopped lucerne, lucerne haylage, and timothy and lucerne haylage. During the free access, goats were given unrestricted access to a particular food for 12 seconds. During the multiple stimulus without replacement, goats were presented with all five foods simultaneously and allowed to make one choice. Once the subject had selected a food by pressing the respective cover with their muzzle, that cover was removed to allow access to that food only. When the subject stopped eating, the cover was replaced - subjects could then select another food. This process was repeated until either all five feeds had been sampled or goats had not made contact with any covers for fifteen seconds. The concurrent schedule test involved making two foods available concurrently. Food delivery was determined by a VI 60s schedule and controlled by a computer software program that was linked to the apparatus. The assessment procedure was arranged so that each food was tested alongside every other food. Data was analysed in terms of the proportion of time and responses allocated to each food. Proportion of time and responses varied considerably depending on the food that was available concurrently.

year: 2018

title: Traditional Knowledge (TK) Labels Transforming Data Infrastructure to Recognise Indigenous Provenance

authors: Hudson, Maui

subjects: Data

abstract: Associate Professor Maui Hudson, KatieLee Riddle and Dr Janette Hamilton-Pearce introduced the latest developments and applications of the Traditional Knowledge Labels and the Local Contexts Hub with examples of use by researchers in Aotearoa New Zealand.

text: Traditional Knowledge (TK) Labels Transforming Data Infrastructure to Recognise Indigenous Provenance Associate Professor Maui Hudson, KatieLee Riddle and Dr Janette Hamilton-Pearce introduced the latest developments and applications of the Traditional Knowledge Labels and the Local Contexts Hub with examples of use by researchers in Aotearoa New Zealand.

year: 2022-09-27