title: ‘Synthetic prospecting’ using an electrospray ionisation mass spectrometry directed survey of the alkylation and arylation chemistry of [Pt₂(μ-S)₂(PPh₃)₄]

authors: Henderson, William

subjects: platinum complexes

abstract: Electrospray ionisation mass spectrometry (ESI-MS) has been used as an analytical tool in a wide-ranging scoping study of the alkylation and arylation reactions of [Pt₂(μ-S)₂(PPh₃)₄]. From these experiments, the factors that influence the formation of different product species – formed by mono- or di-alkylation – are determined. If the alkylating agent is an alkyl chloride or sulfate, monoalkylation followed by dialkylation of the two sulfido groups occurs, dependent on the alkylating power of the reagent used. For example, n-butyl chloride gives solely [Pt₂(μ-S)(μ-SBu)(PPh₃)₄]⁺ while dimethyl sulfate gives [Pt₂(μ-SMe)₂(PPh₃)₄]²⁺. This species, previously unisolated is stable in the absence of good nucleophiles, but the addition of potassium iodide results in rapid conversion to [Pt₂(μ-SMe)₂(PPh₃)₃I]⁺. This iodo complex is also observed from the reaction of [Pt₂(μ-S)₂(PPh₃)₄] with excess MeI, after the initial formation of mono- and di-methylated species. In these reactions, the iodide presumably displaces a phosphine ligand, which is then quaternised by excess alkylating agent. Changing the alkylating agent to a longer chain alkyl iodide or methyl bromide decreases the rate of alkylation of the sulfide in the initially formed [Pt₂(μ-S)(μ-SR)(PPh₃)₄]⁺. Mixed-thiolate species of the type [Pt₂(μ-SMe)(μ-SR)(PPh₃)₄]²⁺ are easily generated by reaction of [Pt²(μ-S)(μ-SR)(PPh₃)₄]⁺ with excess Me₂SO₄ and is also dependent on the avoidance of nucleophiles. Reactions towards α,ω-dialkylating agents are surveyed; the chain length is found to have a dramatic effect on the rate of the second intramolecular cyclisation process, illustrated by a competitive reactivity study involving a mixture of Br(CH₂)₄Br and Br(CH₂)₅Br; on completion of the reaction the former gives [Pt₂{μ-S(CH₂)₄S}(PPh₃)₄]²⁺ while the latter predominantly gives monoalkylated[Pt₂(μ-S){μ-S(CH₂)₅Br}(PPh₃)₄]⁺. The reactivity of o- and p-dihaloxylenes has been explored, with the reaction with p-BrCH₂C₆H₄CH₂Br giving the bridged species [(PPh₃)₄Pt₂(μ-S)(μ-SCH₂C₆H₄CH₂S)(μ-S)Pt₂(PPh₃)₄]²⁺. Arylation reactions of [Pt₂(μ-S)₂(PPh₃)₄] with halobenzenes and 2-bromoheterocyclic compounds (pyridine, thiophene) are also described.

text: ‘Synthetic prospecting’ using an electrospray ionisation mass spectrometry directed survey of the alkylation and arylation chemistry of [Pt₂(μ-S)₂(PPh₃)₄] Electrospray ionisation mass spectrometry (ESI-MS) has been used as an analytical tool in a wide-ranging scoping study of the alkylation and arylation reactions of [Pt₂(μ-S)₂(PPh₃)₄]. From these experiments, the factors that influence the formation of different product species – formed by mono- or di-alkylation – are determined. If the alkylating agent is an alkyl chloride or sulfate, monoalkylation followed by dialkylation of the two sulfido groups occurs, dependent on the alkylating power of the reagent used. For example, n-butyl chloride gives solely [Pt₂(μ-S)(μ-SBu)(PPh₃)₄]⁺ while dimethyl sulfate gives [Pt₂(μ-SMe)₂(PPh₃)₄]²⁺. This species, previously unisolated is stable in the absence of good nucleophiles, but the addition of potassium iodide results in rapid conversion to [Pt₂(μ-SMe)₂(PPh₃)₃I]⁺. This iodo complex is also observed from the reaction of [Pt₂(μ-S)₂(PPh₃)₄] with excess MeI, after the initial formation of mono- and di-methylated species. In these reactions, the iodide presumably displaces a phosphine ligand, which is then quaternised by excess alkylating agent. Changing the alkylating agent to a longer chain alkyl iodide or methyl bromide decreases the rate of alkylation of the sulfide in the initially formed [Pt₂(μ-S)(μ-SR)(PPh₃)₄]⁺. Mixed-thiolate species of the type [Pt₂(μ-SMe)(μ-SR)(PPh₃)₄]²⁺ are easily generated by reaction of [Pt²(μ-S)(μ-SR)(PPh₃)₄]⁺ with excess Me₂SO₄ and is also dependent on the avoidance of nucleophiles. Reactions towards α,ω-dialkylating agents are surveyed; the chain length is found to have a dramatic effect on the rate of the second intramolecular cyclisation process, illustrated by a competitive reactivity study involving a mixture of Br(CH₂)₄Br and Br(CH₂)₅Br; on completion of the reaction the former gives [Pt₂{μ-S(CH₂)₄S}(PPh₃)₄]²⁺ while the latter predominantly gives monoalkylated[Pt₂(μ-S){μ-S(CH₂)₅Br}(PPh₃)₄]⁺. The reactivity of o- and p-dihaloxylenes has been explored, with the reaction with p-BrCH₂C₆H₄CH₂Br giving the bridged species [(PPh₃)₄Pt₂(μ-S)(μ-SCH₂C₆H₄CH₂S)(μ-S)Pt₂(PPh₃)₄]²⁺. Arylation reactions of [Pt₂(μ-S)₂(PPh₃)₄] with halobenzenes and 2-bromoheterocyclic compounds (pyridine, thiophene) are also described.

year: 2006

title: Mental health and legal landscapes

authors: Campion, Michelle Edith

abstract: When it was established early in the twentieth century, Tokanui became part of a network of mental hospitals that were responsible for the care and confinement of the insane and the mentally deficient. At the time of its construction Tokanui was the first new mental hospital commissioned in over 20 years and the first to be built in the central North Island. Of those mental hospitals operating in 1912 all, except Ashburn Hall (the country's only private institution), were government controlled and funded. State dominance in the management of mental abnormality was the result of an unofficial policy which followed English precedent, favouring government intervention in the belief that it produced beneficial results and which endorsed the conviction that government responsibility for such matters could not be divested to a third party. This position was strengthened by the paucity of a prosperous philanthropic class who would otherwise have bridged the gulf between demand and supply under the auspices of charity. The essence of this philosophy was reflected in the early nineteenth and twentieth-century legislation which governed the development and management of New Zealand's mental hospitals.

text: Mental health and legal landscapes When it was established early in the twentieth century, Tokanui became part of a network of mental hospitals that were responsible for the care and confinement of the insane and the mentally deficient. At the time of its construction Tokanui was the first new mental hospital commissioned in over 20 years and the first to be built in the central North Island. Of those mental hospitals operating in 1912 all, except Ashburn Hall (the country's only private institution), were government controlled and funded. State dominance in the management of mental abnormality was the result of an unofficial policy which followed English precedent, favouring government intervention in the belief that it produced beneficial results and which endorsed the conviction that government responsibility for such matters could not be divested to a third party. This position was strengthened by the paucity of a prosperous philanthropic class who would otherwise have bridged the gulf between demand and supply under the auspices of charity. The essence of this philosophy was reflected in the early nineteenth and twentieth-century legislation which governed the development and management of New Zealand's mental hospitals.

year: 2012

title: Homai raa. Kia purutia, kia hereherea, taawhiwhi taamau. Ka pai. Taawhiwhi  taumau, he tauira waiora a Waikato : The creation of a Waikato-specific Maaori health model

authors: Haggie, Marrin Brian Pikitawhaki

subjects: Taawhiwhi Taamau

abstract: This Doctoral rangahau (research) sought to create a Maaori (Indigenous people of New Zealand) health model specific to the health needs and desires of the people of Waikato (The collective name of the tribes of the Waikato basin). Globally, minority populations (including Maaori) are consistently and disproportionately over represented in many health, education and incarceration statistics. Colonisation, oppression and racial prejudices have been identified as the root causes for the statistical imbalances prevalent in society. Indigenous populations have endured suffering caused by disconnection from heritage, traditional practices, ancestral beliefs and the natural environment. All are consequences of legislative enforcement and an oppressive, colonialist attitude that patronises indigenous populations (i.e., that assumes the coloniser knows what is best for the colonised). 

For the majority of colonisation, the health models and frameworks intended to benefit indigenous peoples, yet designed and implemented by colonial based, oppressive governments and by institutions rooted in colonialist ideals, have consistently failed to provide and deliver health and wellness for indigenous peoples. The fact that indigenous peoples’ health continues to be poorer than their non-indigenous counterparts, in the majority of health measures, suggests models and frameworks designed by non-indigenous people do not work for indigenous populations. This has led to an emergence of indigenous and minority populations’ movements seeking to emancipate themselves from the shackles of colonial oppression. 

Pioneering health models and frameworks designed to counter the failures of those designed by the oppressor have provided salvation for indigenous peoples and have allowed the voices of minority populations to be heard in the health and wellbeing context; however the majority of these models have been overly generic. Yet, they have provided foundations that now must be built upon to enable a focus on what specific populations require to ensure their health and lifestyle ideals are supported and strengthened.

As whaanau (family), marae (place of gathering and belonging for interrelated families), hapuu (subtribe), and as an iwi (tribe), Waikato have a responsibility to our taiao (natural environment), ourselves and to future generations to ensure the health of Waikato and that Waikatotanga (Waikato culture and practice) continues to grow, prosper, and flourish. Therefore, as a polity we must assert the control and direction of our iwi by determining and creating our own models and frameworks to ensure the survival, the growth, and the success of our people.

This Rangahau Kaupapa Waikato (Waikato focused research) is centered on the question ‘What elements must be considered in the creation and the application of a Waikato-specific, Maaori health model?’ Contemporary literature and research regarding health and the impacts on Indigenous and Maaori health specifically, was used to review the successes and failures of contemporary health models. 

Supported and framed by a Rangahau Kaupapa Maaori (Maaori focused research) approach, this Rangahau Kaupapa Waikato utilised Waikato koorero (stories), beliefs, practices and methodologies, interspersed with Qualitative Methodology and Thematic Analysis. Fourteen semi-structured interviews with tribal leaders and holders of tribal knowledge, referred to as taniwha, were conducted. Each taniwha shared their knowledge, understandings, and experiences to inform and contribute to the creation of a holistic health model specific to the iwi of Waikato.

The findings illustrate continued connection to the Waikato awa (river), the taiao (natural environment), wairuatanga (spirituality), ancestral knowledge and practices, the Kiingitanga (Maaori King Movement) and to the iwi itself are critical to the perpetuation of the waiora (health) of the Waikato iwi and of Waikatotanga in its multiple forms.

The model created as the primary outcome of this research, The Taawhiwhi Taamau Model of Waiora (Taawhiwhi Taamau), was designed to act as a vehicle which seeks to enable individual iwi members, and the polities that they belong, to achieve Mana-motuhake (autonomy) and self-determination of their own health. Taawhiwhi Taamau seeks to inform its adopters that Mana-motuhake can be achieved without having to compromise any of the tikanga (protocol) and kawa (custom) of our iwi and of our ancestors in favour of colonial government introduced, western ideals. Thereby removing the oppressor from the implementation and application of health. 

Taawhiwhi Taamau is a health model entrenched in Waikatotanga that utilises the beliefs and practices of our ancestors, and subsequently, our iwi to facilitate Tupuna (ancestor) Guided Living. The model encourages the individual iwi member to build solid foundations of waiora, seek knowledge and understanding of our tupuna, and use the experiences in life to act as taniwha for others seeking guidance, knowledge, connection, understanding and waiora. 

The adoption and practice of Taawhiwhi Taamau suggests individuals will find a new, refreshed connection to tupuna, maatauranga (wisdom, knowledge), wairuatanga and Waikatotanga, therefore, increasing waiora. Increased waiora of the individual increases the waiora and the capacity of one’s whaanau, marae and hapuu thereby increasing the waiora and the capacity of the iwi. Increased waiora and capacity of the iwi increases the likelihood of Waikatotanga, maatauranga, wairuatanga and, thus, the perpetuation of Tupuna Guided Living. Consequently, encapsulating the essence of Taawhiwhi Taamau as a model and as the lesson learned in the Pai Maarire Te Kura o te Ahiahi, ‘Homai ra, kia purutia, kia hereherea, taawhiwhi taamau. Ka Pai’.

text: Homai raa. Kia purutia, kia hereherea, taawhiwhi taamau. Ka pai. Taawhiwhi  taumau, he tauira waiora a Waikato : The creation of a Waikato-specific Maaori health model This Doctoral rangahau (research) sought to create a Maaori (Indigenous people of New Zealand) health model specific to the health needs and desires of the people of Waikato (The collective name of the tribes of the Waikato basin). Globally, minority populations (including Maaori) are consistently and disproportionately over represented in many health, education and incarceration statistics. Colonisation, oppression and racial prejudices have been identified as the root causes for the statistical imbalances prevalent in society. Indigenous populations have endured suffering caused by disconnection from heritage, traditional practices, ancestral beliefs and the natural environment. All are consequences of legislative enforcement and an oppressive, colonialist attitude that patronises indigenous populations (i.e., that assumes the coloniser knows what is best for the colonised). 

For the majority of colonisation, the health models and frameworks intended to benefit indigenous peoples, yet designed and implemented by colonial based, oppressive governments and by institutions rooted in colonialist ideals, have consistently failed to provide and deliver health and wellness for indigenous peoples. The fact that indigenous peoples’ health continues to be poorer than their non-indigenous counterparts, in the majority of health measures, suggests models and frameworks designed by non-indigenous people do not work for indigenous populations. This has led to an emergence of indigenous and minority populations’ movements seeking to emancipate themselves from the shackles of colonial oppression. 

Pioneering health models and frameworks designed to counter the failures of those designed by the oppressor have provided salvation for indigenous peoples and have allowed the voices of minority populations to be heard in the health and wellbeing context; however the majority of these models have been overly generic. Yet, they have provided foundations that now must be built upon to enable a focus on what specific populations require to ensure their health and lifestyle ideals are supported and strengthened.

As whaanau (family), marae (place of gathering and belonging for interrelated families), hapuu (subtribe), and as an iwi (tribe), Waikato have a responsibility to our taiao (natural environment), ourselves and to future generations to ensure the health of Waikato and that Waikatotanga (Waikato culture and practice) continues to grow, prosper, and flourish. Therefore, as a polity we must assert the control and direction of our iwi by determining and creating our own models and frameworks to ensure the survival, the growth, and the success of our people.

This Rangahau Kaupapa Waikato (Waikato focused research) is centered on the question ‘What elements must be considered in the creation and the application of a Waikato-specific, Maaori health model?’ Contemporary literature and research regarding health and the impacts on Indigenous and Maaori health specifically, was used to review the successes and failures of contemporary health models. 

Supported and framed by a Rangahau Kaupapa Maaori (Maaori focused research) approach, this Rangahau Kaupapa Waikato utilised Waikato koorero (stories), beliefs, practices and methodologies, interspersed with Qualitative Methodology and Thematic Analysis. Fourteen semi-structured interviews with tribal leaders and holders of tribal knowledge, referred to as taniwha, were conducted. Each taniwha shared their knowledge, understandings, and experiences to inform and contribute to the creation of a holistic health model specific to the iwi of Waikato.

The findings illustrate continued connection to the Waikato awa (river), the taiao (natural environment), wairuatanga (spirituality), ancestral knowledge and practices, the Kiingitanga (Maaori King Movement) and to the iwi itself are critical to the perpetuation of the waiora (health) of the Waikato iwi and of Waikatotanga in its multiple forms.

The model created as the primary outcome of this research, The Taawhiwhi Taamau Model of Waiora (Taawhiwhi Taamau), was designed to act as a vehicle which seeks to enable individual iwi members, and the polities that they belong, to achieve Mana-motuhake (autonomy) and self-determination of their own health. Taawhiwhi Taamau seeks to inform its adopters that Mana-motuhake can be achieved without having to compromise any of the tikanga (protocol) and kawa (custom) of our iwi and of our ancestors in favour of colonial government introduced, western ideals. Thereby removing the oppressor from the implementation and application of health. 

Taawhiwhi Taamau is a health model entrenched in Waikatotanga that utilises the beliefs and practices of our ancestors, and subsequently, our iwi to facilitate Tupuna (ancestor) Guided Living. The model encourages the individual iwi member to build solid foundations of waiora, seek knowledge and understanding of our tupuna, and use the experiences in life to act as taniwha for others seeking guidance, knowledge, connection, understanding and waiora. 

The adoption and practice of Taawhiwhi Taamau suggests individuals will find a new, refreshed connection to tupuna, maatauranga (wisdom, knowledge), wairuatanga and Waikatotanga, therefore, increasing waiora. Increased waiora of the individual increases the waiora and the capacity of one’s whaanau, marae and hapuu thereby increasing the waiora and the capacity of the iwi. Increased waiora and capacity of the iwi increases the likelihood of Waikatotanga, maatauranga, wairuatanga and, thus, the perpetuation of Tupuna Guided Living. Consequently, encapsulating the essence of Taawhiwhi Taamau as a model and as the lesson learned in the Pai Maarire Te Kura o te Ahiahi, ‘Homai ra, kia purutia, kia hereherea, taawhiwhi taamau. Ka Pai’.

year: 2021