title: Stable diplatinum complexes with functional thiolato bridges from dialkylation of [Pt₂(μ-S)₂(P–P)₂] [P–P = 2 × PPh₃, Ph₂P(CH₂)₃PPh₂]

authors: Chong, Siew Huay

subjects: chemistry

abstract: The normally robust monoalkylated complexes [Pt₂(μ-S)(μ-SR)(PPh₃)₄]⁺ can be activated towards further alkylation. Dialkylated complexes [Pt₂(μ-SR)₂(P–P)₂]²⁺ (P–P = 2 × PPh₃, Ph₂P(CH₂)₃PPh₂) can be stabilized and isolated by the use of electron-rich and aromatic halogenated substituents R [e.g. 3-(2-bromoethyl)indole and 2-bromo-4 -phenylacetophenone] and 1,3-bis(diphenylphosphino)propane [Ph₂P(CH₂)₃PPh₂ or dppp] which enhances the nucleophilicity of the {Pt₂(μ-S)₂} core. This strategy led to the activation of [Pt₂(μ-S)(μ-SR)(PPh₃)₄]⁺ towards R–X as well as isolation and crystallographic elucidation of [Pt₂(μ-SC₁₀H₁₀N)₂(PPh₃)₄](PF₆)₂ ( 2a), [Pt₂(μ-SCH₂C(O)C₆H₄C₆H₅)₂(PPh₃)₄](PF₆)₂ ( 2b), and a range of functionalized-thiolato bridged complexes such as [Pt₂(μ-SR)₂(dppp)₂](PF₆)₂ [R = –CH₂C₆H₅ ( 8a), –CH₂CHCH₂ ( 8b) and –CH₂CN ( 8c)]. The stepwise alkylation process is conveniently monitored by Electrospray Ionisation Mass Spectrometry, allowing for a direct qualitative comparison of the nucleophilicity of [Pt₂(μ-S)₂(P–P)₂], thereby guiding the bench-top synthesis of some products observed spectroscopically.

text: Stable diplatinum complexes with functional thiolato bridges from dialkylation of [Pt₂(μ-S)₂(P–P)₂] [P–P = 2 × PPh₃, Ph₂P(CH₂)₃PPh₂] The normally robust monoalkylated complexes [Pt₂(μ-S)(μ-SR)(PPh₃)₄]⁺ can be activated towards further alkylation. Dialkylated complexes [Pt₂(μ-SR)₂(P–P)₂]²⁺ (P–P = 2 × PPh₃, Ph₂P(CH₂)₃PPh₂) can be stabilized and isolated by the use of electron-rich and aromatic halogenated substituents R [e.g. 3-(2-bromoethyl)indole and 2-bromo-4 -phenylacetophenone] and 1,3-bis(diphenylphosphino)propane [Ph₂P(CH₂)₃PPh₂ or dppp] which enhances the nucleophilicity of the {Pt₂(μ-S)₂} core. This strategy led to the activation of [Pt₂(μ-S)(μ-SR)(PPh₃)₄]⁺ towards R–X as well as isolation and crystallographic elucidation of [Pt₂(μ-SC₁₀H₁₀N)₂(PPh₃)₄](PF₆)₂ ( 2a), [Pt₂(μ-SCH₂C(O)C₆H₄C₆H₅)₂(PPh₃)₄](PF₆)₂ ( 2b), and a range of functionalized-thiolato bridged complexes such as [Pt₂(μ-SR)₂(dppp)₂](PF₆)₂ [R = –CH₂C₆H₅ ( 8a), –CH₂CHCH₂ ( 8b) and –CH₂CN ( 8c)]. The stepwise alkylation process is conveniently monitored by Electrospray Ionisation Mass Spectrometry, allowing for a direct qualitative comparison of the nucleophilicity of [Pt₂(μ-S)₂(P–P)₂], thereby guiding the bench-top synthesis of some products observed spectroscopically.

year: 2007

title: Headteachers’ readings of and responses to disadvantaged contexts: evidence from English primary schools

authors: Lupton, Ruth

subjects: schools

abstract: Existing research demonstrates the impact of context on school organisation and management, curriculum and pedagogy and on student peer relations. New developments in English education policy will devolve more responsibility for dealing with these issues to headteachers. Headteachers' readings of their contexts and the responses that they make are thus of increasing interest. This paper draws on interviews with eight headteachers of less advantaged English primary schools to explore how they understand and articulate the contexts in which their schools operate and how this knowledge is translated into strategies for organising curriculum, pedagogy and other school processes. These headteachers observed context through the lens of the behaviour of parents and children in relation to school, contrasting it with an assumed middle-class normality. More critical perspectives on families' social and economic position or on the contribution of school practice to educational exclusion were largely absent. School responses were many and varied but, given the constraints of budgets, market and performative pressures, were unlikely to substantially transform the educational experiences and outcomes of disadvantaged students. We point to the continuing need for more contextualised funding mechanisms and policies to improve schools in disadvantaged areas and also, in the light of devolution to schools, to the need to develop mechanisms of support to headteachers to help them to develop critical understandings of context and to reflect on school process and practices in the light of these understandings.

text: Headteachers’ readings of and responses to disadvantaged contexts: evidence from English primary schools Existing research demonstrates the impact of context on school organisation and management, curriculum and pedagogy and on student peer relations. New developments in English education policy will devolve more responsibility for dealing with these issues to headteachers. Headteachers' readings of their contexts and the responses that they make are thus of increasing interest. This paper draws on interviews with eight headteachers of less advantaged English primary schools to explore how they understand and articulate the contexts in which their schools operate and how this knowledge is translated into strategies for organising curriculum, pedagogy and other school processes. These headteachers observed context through the lens of the behaviour of parents and children in relation to school, contrasting it with an assumed middle-class normality. More critical perspectives on families' social and economic position or on the contribution of school practice to educational exclusion were largely absent. School responses were many and varied but, given the constraints of budgets, market and performative pressures, were unlikely to substantially transform the educational experiences and outcomes of disadvantaged students. We point to the continuing need for more contextualised funding mechanisms and policies to improve schools in disadvantaged areas and also, in the light of devolution to schools, to the need to develop mechanisms of support to headteachers to help them to develop critical understandings of context and to reflect on school process and practices in the light of these understandings.

year: 2013

title: Māori and Dementia: Māori health professionals’ perceptions of dementia, support offered and suggested improvements

authors: Townsend, Marie

subjects: dementia

abstract: E iti noa ana, nā te aroha (It is the giving that counts and not the size of the gift) The purpose of this thesis was to investigate the perceptions of Māori health professionals about Māori elders and dementia. The study aimed to describe: Māori health care providers’ understandings of dementia; traditional versus contemporary understandings; how cultural beliefs affect experience; how Māori cope with dementia; key issues relevant to Māori people with dementia; and how services can be improved to meet the needs of aged Māori. The usefulness and possible cultural adaptation of the biomedical model has been explored within the context of a Māori worldview and the perceptions of participants. Semi-structured and in-depth interviews were conducted with eight mental health professionals and one caregiver. The information gathered at interviews was recorded within verbatim transcripts, which were written and returned to the participants for feedback. A qualitative data analysis was carried out on the approved transcripts. The main findings suggest that Māori health professionals recognise that many Māori perceive dementia both from a traditional cultural perspective, associated with spirituality as well as a holistic understanding of wellness. Key issues identified by participants were: that there is fear associated with mental health facilities; the exclusion of cultural values and understandings from service providers is detrimental to the wellbeing of Māori elders; Māori do not understand the symptoms typically associated with dementia as an illness; there is a need for information and education within an appropriate frame for whānau; disjointed and multiple service providers inhibits Māori from accessing facilities offered; and that there is a real need for further services. It was considered important that mental health services are culturally appropriate, show respect for Māori values; are coordinated and sensitive; encourage and continue the development of a Māori mental health workforce; and further develop kaupapa Māori services for Māori elders. The main implication of this research is that further investigation into Māori and dementia is required. Recommendations are made with a view towards better addressing some of the mental health needs of Māori elders.

text: Māori and Dementia: Māori health professionals’ perceptions of dementia, support offered and suggested improvements E iti noa ana, nā te aroha (It is the giving that counts and not the size of the gift) The purpose of this thesis was to investigate the perceptions of Māori health professionals about Māori elders and dementia. The study aimed to describe: Māori health care providers’ understandings of dementia; traditional versus contemporary understandings; how cultural beliefs affect experience; how Māori cope with dementia; key issues relevant to Māori people with dementia; and how services can be improved to meet the needs of aged Māori. The usefulness and possible cultural adaptation of the biomedical model has been explored within the context of a Māori worldview and the perceptions of participants. Semi-structured and in-depth interviews were conducted with eight mental health professionals and one caregiver. The information gathered at interviews was recorded within verbatim transcripts, which were written and returned to the participants for feedback. A qualitative data analysis was carried out on the approved transcripts. The main findings suggest that Māori health professionals recognise that many Māori perceive dementia both from a traditional cultural perspective, associated with spirituality as well as a holistic understanding of wellness. Key issues identified by participants were: that there is fear associated with mental health facilities; the exclusion of cultural values and understandings from service providers is detrimental to the wellbeing of Māori elders; Māori do not understand the symptoms typically associated with dementia as an illness; there is a need for information and education within an appropriate frame for whānau; disjointed and multiple service providers inhibits Māori from accessing facilities offered; and that there is a real need for further services. It was considered important that mental health services are culturally appropriate, show respect for Māori values; are coordinated and sensitive; encourage and continue the development of a Māori mental health workforce; and further develop kaupapa Māori services for Māori elders. The main implication of this research is that further investigation into Māori and dementia is required. Recommendations are made with a view towards better addressing some of the mental health needs of Māori elders.

year: 2011