title: Further studies on the coordination chemistry of [Pt₂(μ-S)₂(PPh₃)₄] towards indium(III) substrates

authors: Henderson, William

subjects: Platinum complexes

abstract: The reactivity of the metalloligand [Pt₂(μ-S)₂(PPh₃)₄] towards a variety of indium(III) substrates has been explored. Reaction with excess In(NO₃)₃ and halide (KBr or NaI) gave the four-coordinate adducts [Pt₂(μ-S)₂(PPh₃)₄InX₂]⁺[InX₄]⁻ (X = Br, I). An X-ray structure determination on the iodo complex revealed a slightly distorted tetrahedral coordination geometry at indium. In contrast, reaction of [Pt₂(μ-S)₂(PPh₃)₄] with indium(III) chloride was more complex; the ion [Pt₂(μ-S)₂(PPh₃)₄InCl₂]⁺ was initially observed in solution (using ESI mass spectrometry), and isolated as its BPh₄⁻ salt. Analysis of [Pt₂(μ-S)₂(PPh₃)₄InCl₂]⁺[BPh₄]⁻ by ESI MS showed the parent cation when analysed in MeCN solution. However in solutions containing methanol, partial solvolysis occurred to give the di-indium species [{Pt₂(μ-S)₂(PPh₃)₄InCl(OMe)}₂]²⁺ (proposed to contain an In₂(μ-OMe)₂ unit with five-coordinate indium) and its fragment ion [Pt₂ (μ-S)₂(PPh₃)₄InCl(OMe)]⁺. Reaction of [Pt₂(μ-S)₂(PPh₃)₄] with InCl₃•3H₂O, 8-hydroxyquinoline (HQ) and trimethylamine in methanol gave the adduct [Pt₂(μ-S)₂(PPh₃)₄InQ₂]⁺, isolated as its PF₆⁻ salt. The same cationic complex is formed when [Pt₂(μ-S)₂(PPh₃)₄] is reacted with InQ₃ in methanol, but in this case the product is contaminated with the mononuclear complex [(Ph₃P)₂PtQ]⁺ formed by disintegration of the trinuclear complex [Pt₂(μ-S)₂(PPh₃)₄InQ₂]⁻ with byproduct Q⁻. [(Ph₃P)₂PtQ]⁺BPh₄⁻ was independently prepared from cis-[PtCl₂(PPh₃)₂] and HQ/Me₃N, and is the first example of a platinum 8-hydroxyquinolinate complex containing phosphine ligands.

text: Further studies on the coordination chemistry of [Pt₂(μ-S)₂(PPh₃)₄] towards indium(III) substrates The reactivity of the metalloligand [Pt₂(μ-S)₂(PPh₃)₄] towards a variety of indium(III) substrates has been explored. Reaction with excess In(NO₃)₃ and halide (KBr or NaI) gave the four-coordinate adducts [Pt₂(μ-S)₂(PPh₃)₄InX₂]⁺[InX₄]⁻ (X = Br, I). An X-ray structure determination on the iodo complex revealed a slightly distorted tetrahedral coordination geometry at indium. In contrast, reaction of [Pt₂(μ-S)₂(PPh₃)₄] with indium(III) chloride was more complex; the ion [Pt₂(μ-S)₂(PPh₃)₄InCl₂]⁺ was initially observed in solution (using ESI mass spectrometry), and isolated as its BPh₄⁻ salt. Analysis of [Pt₂(μ-S)₂(PPh₃)₄InCl₂]⁺[BPh₄]⁻ by ESI MS showed the parent cation when analysed in MeCN solution. However in solutions containing methanol, partial solvolysis occurred to give the di-indium species [{Pt₂(μ-S)₂(PPh₃)₄InCl(OMe)}₂]²⁺ (proposed to contain an In₂(μ-OMe)₂ unit with five-coordinate indium) and its fragment ion [Pt₂ (μ-S)₂(PPh₃)₄InCl(OMe)]⁺. Reaction of [Pt₂(μ-S)₂(PPh₃)₄] with InCl₃•3H₂O, 8-hydroxyquinoline (HQ) and trimethylamine in methanol gave the adduct [Pt₂(μ-S)₂(PPh₃)₄InQ₂]⁺, isolated as its PF₆⁻ salt. The same cationic complex is formed when [Pt₂(μ-S)₂(PPh₃)₄] is reacted with InQ₃ in methanol, but in this case the product is contaminated with the mononuclear complex [(Ph₃P)₂PtQ]⁺ formed by disintegration of the trinuclear complex [Pt₂(μ-S)₂(PPh₃)₄InQ₂]⁻ with byproduct Q⁻. [(Ph₃P)₂PtQ]⁺BPh₄⁻ was independently prepared from cis-[PtCl₂(PPh₃)₂] and HQ/Me₃N, and is the first example of a platinum 8-hydroxyquinolinate complex containing phosphine ligands.

year: 2011

title: Member voice and influence: A study of cooperative governance in the Australasian dairy industry

authors: Malherbe, Alexander Stephen

subjects: Cooperative

abstract: Member governance can be characterised as the voice and influence that members have in their cooperative. The voice is related to the tangible control mechanisms available to cooperative members, and the influence ingredient is more often the intangible relational aspect of a member’s connection. There are layers of governance that build on each other to form the foundation of cooperative members rights or voice and influence; these include Cooperative Principles, Cooperative Law, and the Cooperative Constitutional Document. The collective aim is to mitigate many of the known cooperative governance challenges. Notwithstanding all the theoretical layers of governance, the actual members’ perceptions and the reality of their participation in their cooperative can affect the quality of member governance in a cooperative. 
The cooperative principles are the foundational ingredient for member-organisation governance. In many regions, the principles are applied in the creation of cooperative law. In some regions countries base their legislation fully or partially on the International Cooperative Alliance (ICA) set of seven principles; other regions engage with a different set of principles such as the United States Department of Agriculture (USDA) set of three principles, while in other countries the link between cooperative law and cooperative principles is less visible. 
An examination of which principles are employed in constructing the legislation that governs cooperatives in a particular region is crucial as it provides us with a base for analysis. Cooperative law differs from country to country, with some cooperative law being comprehensive while other countries cooperative laws are not well defined. The answer as to which approach is more effective is examined in this thesis.
Similarly, cooperative law usually forms the foundation that mandates provisions in the originating document, the cooperative constitution. The purpose of the constitution is to protect the rights of cooperative members at a higher level. It is usually tailored for each cooperative; however, the base provisions that are mandated within the cooperative law are often common. A sample of Australasian cooperatives is used to analyse and discover how the law influences member rights. 
Notwithstanding the layers of protection afforded to members, it is widely acknowledged that cooperatives face governance challenges. Besides common governance challenges that affect most organisational forms, cooperatives confront other unique problems. The combination of cooperative principles, law, and the constitutional document is, in essence, the cooperative policy framework for an individual cooperative within a specific country. In theory, the application of the framework should significantly mitigate most cooperative governance challenges. An analysis of the level of mitigation is necessary to understand the effectiveness of the Australasian cooperative policy frameworks. 
Apart from the rights of cooperative members, the actual engagement that a member has with their cooperative can mitigate shortcomings in both voice and influence. The relationship that a member has with their cooperative is an essential aspect of governance in that good engagement can overcome poor governance processes while the converse is not always true. An in-depth understanding of member views, perceptions, and requirements is essential for those seeking to develop an effective engagement structure that can overcome governance shortcomings within dairy cooperatives in Australasia. This thesis explores the experience of the governance environment through the member-lens, specifically to understand the strengths and weaknesses of each cooperative's governance and engagement model when compared to the other dairy cooperatives in this study.
This thesis analyses each of the supporting governance layers that contribute to maximising member voice and influence to answer the overarching research questions: What are the governance challenges and opportunities facing Australasian dairy cooperatives, and what governance elements contribute to an effective cooperative governance framework? Furthermore, the thesis seeks to answer fundamental cooperative member governance questions; Do the principles support the law when used in crafting policy for cooperatives? Does the law protect the members’ rights to the extent that was the original intention of the policymakers? Does the constitutional document have the correct provisions, and are these mandated, to protect the members' voice? Do these layers of governance collectively mitigate the challenges that might contribute to a decline in the cooperative? Finally, what are the governance and engagement perceptions of members on their voice and influence, and how well is this functioning in Australasia?
There is little research that seeks to understand the role of cooperative principles and policy in the governance of a cooperative and what the reality of cooperative member participation is in Australasian dairy cooperative governance. This thesis contributes to the theoretical understanding of how cooperative principles influence the law and the associated governance documents to minimise the governance challenges of cooperatives. Additionally, this thesis contributes to a practical understanding of the effectiveness of the implementation of cooperative governance in the Australasian dairy context through the member-lens.

text: Member voice and influence: A study of cooperative governance in the Australasian dairy industry Member governance can be characterised as the voice and influence that members have in their cooperative. The voice is related to the tangible control mechanisms available to cooperative members, and the influence ingredient is more often the intangible relational aspect of a member’s connection. There are layers of governance that build on each other to form the foundation of cooperative members rights or voice and influence; these include Cooperative Principles, Cooperative Law, and the Cooperative Constitutional Document. The collective aim is to mitigate many of the known cooperative governance challenges. Notwithstanding all the theoretical layers of governance, the actual members’ perceptions and the reality of their participation in their cooperative can affect the quality of member governance in a cooperative. 
The cooperative principles are the foundational ingredient for member-organisation governance. In many regions, the principles are applied in the creation of cooperative law. In some regions countries base their legislation fully or partially on the International Cooperative Alliance (ICA) set of seven principles; other regions engage with a different set of principles such as the United States Department of Agriculture (USDA) set of three principles, while in other countries the link between cooperative law and cooperative principles is less visible. 
An examination of which principles are employed in constructing the legislation that governs cooperatives in a particular region is crucial as it provides us with a base for analysis. Cooperative law differs from country to country, with some cooperative law being comprehensive while other countries cooperative laws are not well defined. The answer as to which approach is more effective is examined in this thesis.
Similarly, cooperative law usually forms the foundation that mandates provisions in the originating document, the cooperative constitution. The purpose of the constitution is to protect the rights of cooperative members at a higher level. It is usually tailored for each cooperative; however, the base provisions that are mandated within the cooperative law are often common. A sample of Australasian cooperatives is used to analyse and discover how the law influences member rights. 
Notwithstanding the layers of protection afforded to members, it is widely acknowledged that cooperatives face governance challenges. Besides common governance challenges that affect most organisational forms, cooperatives confront other unique problems. The combination of cooperative principles, law, and the constitutional document is, in essence, the cooperative policy framework for an individual cooperative within a specific country. In theory, the application of the framework should significantly mitigate most cooperative governance challenges. An analysis of the level of mitigation is necessary to understand the effectiveness of the Australasian cooperative policy frameworks. 
Apart from the rights of cooperative members, the actual engagement that a member has with their cooperative can mitigate shortcomings in both voice and influence. The relationship that a member has with their cooperative is an essential aspect of governance in that good engagement can overcome poor governance processes while the converse is not always true. An in-depth understanding of member views, perceptions, and requirements is essential for those seeking to develop an effective engagement structure that can overcome governance shortcomings within dairy cooperatives in Australasia. This thesis explores the experience of the governance environment through the member-lens, specifically to understand the strengths and weaknesses of each cooperative's governance and engagement model when compared to the other dairy cooperatives in this study.
This thesis analyses each of the supporting governance layers that contribute to maximising member voice and influence to answer the overarching research questions: What are the governance challenges and opportunities facing Australasian dairy cooperatives, and what governance elements contribute to an effective cooperative governance framework? Furthermore, the thesis seeks to answer fundamental cooperative member governance questions; Do the principles support the law when used in crafting policy for cooperatives? Does the law protect the members’ rights to the extent that was the original intention of the policymakers? Does the constitutional document have the correct provisions, and are these mandated, to protect the members' voice? Do these layers of governance collectively mitigate the challenges that might contribute to a decline in the cooperative? Finally, what are the governance and engagement perceptions of members on their voice and influence, and how well is this functioning in Australasia?
There is little research that seeks to understand the role of cooperative principles and policy in the governance of a cooperative and what the reality of cooperative member participation is in Australasian dairy cooperative governance. This thesis contributes to the theoretical understanding of how cooperative principles influence the law and the associated governance documents to minimise the governance challenges of cooperatives. Additionally, this thesis contributes to a practical understanding of the effectiveness of the implementation of cooperative governance in the Australasian dairy context through the member-lens.

year: 2020

title: Assessment of effects of proposed treated wastewater discharge to the Te Arikiroa Thermal Channel and Sulphur Bay (Lake Rotorua)

authors: Dada, Ayokunle Christopher

abstract: After 2019, irrigation operations at the Land Treatment System (LTS) in the Whakarewarewa Forest are scheduled to cease. A number of options and locations have been considered for the discharge of the treated wastewater when the current discharge consent ceases. Following consultations and technical assessments, the preferred option of Rotorua Lakes Council is to upgrade the existing plant to a full Membrane Bioreactor Plant with the addition of an Ultraviolet Disinfection System (or alternative treatment to achieve an equivalent performance in terms of treated wastewater quality). Under this arrangement, wastewater would be subjected to biological, chemical and physical treatment processes, and the treated wastewater discharged through Te Arikiroa Thermal Channel to Sulphur Bay. Rotorua Lakes Council is thus undertaking an environmental impact assessment study to determine the effects of discharging treated wastewater to the thermal channel and Puarenga Bay (Lake Rotorua), with particular reference to aesthetic, water quality and ecological considerations. These considerations include potential effects related to faecal indicator bacteria, nutrient concentrations, metals, dissolved oxygen, and taonga species (native species of cultural significance).
The assessment focused on:
(i)	The projected treated wastewater characteristics;

(ii)	Existing conditions of the receiving water;

(iii)	The sensitivity of the receiving water and the impact of the proposed discharge on water quality and taonga species (native species of cultural significance) in Te Arikiroa Thermal Channel and Sulphur Bay.

The main techniques used to inform the assessment in this study were:
1) Analysis of historical water quality data, 2011-2014;
2) Collection of additional water quality data at Te Arikiroa Thermal Channel and Sulphur Bay and along a transect to quantify spatial variability (sampling in 2016 and 2017);
3) Mass balance dilution modelling to predict water quality in the Te Arikiroa Thermal Channel and Sulphur Bay (Lake Rotorua), at a site outside of the assumed mixing zone;
4) Lake ecosystem modelling conducted by Abell et al. (2015) to assess effects related to eutrophication;
5) Background review of biological information and field investigations for taonga species at Sulphur Bay and Te Arikiroa Thermal Channel (2017).

text: Assessment of effects of proposed treated wastewater discharge to the Te Arikiroa Thermal Channel and Sulphur Bay (Lake Rotorua) After 2019, irrigation operations at the Land Treatment System (LTS) in the Whakarewarewa Forest are scheduled to cease. A number of options and locations have been considered for the discharge of the treated wastewater when the current discharge consent ceases. Following consultations and technical assessments, the preferred option of Rotorua Lakes Council is to upgrade the existing plant to a full Membrane Bioreactor Plant with the addition of an Ultraviolet Disinfection System (or alternative treatment to achieve an equivalent performance in terms of treated wastewater quality). Under this arrangement, wastewater would be subjected to biological, chemical and physical treatment processes, and the treated wastewater discharged through Te Arikiroa Thermal Channel to Sulphur Bay. Rotorua Lakes Council is thus undertaking an environmental impact assessment study to determine the effects of discharging treated wastewater to the thermal channel and Puarenga Bay (Lake Rotorua), with particular reference to aesthetic, water quality and ecological considerations. These considerations include potential effects related to faecal indicator bacteria, nutrient concentrations, metals, dissolved oxygen, and taonga species (native species of cultural significance).
The assessment focused on:
(i)	The projected treated wastewater characteristics;

(ii)	Existing conditions of the receiving water;

(iii)	The sensitivity of the receiving water and the impact of the proposed discharge on water quality and taonga species (native species of cultural significance) in Te Arikiroa Thermal Channel and Sulphur Bay.

The main techniques used to inform the assessment in this study were:
1) Analysis of historical water quality data, 2011-2014;
2) Collection of additional water quality data at Te Arikiroa Thermal Channel and Sulphur Bay and along a transect to quantify spatial variability (sampling in 2016 and 2017);
3) Mass balance dilution modelling to predict water quality in the Te Arikiroa Thermal Channel and Sulphur Bay (Lake Rotorua), at a site outside of the assumed mixing zone;
4) Lake ecosystem modelling conducted by Abell et al. (2015) to assess effects related to eutrophication;
5) Background review of biological information and field investigations for taonga species at Sulphur Bay and Te Arikiroa Thermal Channel (2017).

year: 2018