title: Some Ruthenium Derivatives of Penta-1,4-diyn-3-one

authors: Bruce, Michael I.

abstract: The reaction between Ru(C≡CH)(dppe)Cp* (1) and oxalyl chloride affords ({Ru(dppe)Cp*}C≡C)₂CO (2) in 72% yield. Methylation (MeOTf) of 2 occurs first on the carbonyl oxygen, affording [({Ru(dppe)Cp*}C≡C)2C(OMe)]OTf ([3]OTf). A second methylation of [3]⁺ on the alkynyl Cβ proceeds slowly, affording [{Cp*(dppe)Ru}CCMeC(OMe)CC{Ru(dppe)Cp*}][OTf]₂ ([4][OTf]₂), whereas protonation of [3]+ occurs readily to give crystallographically characterized [{Cp*(dppe)Ru}CCHC(OMe)CC{Ru(dppe)Cp*}][OTf]₂ ([5][OTf]₂). The molecular structures of [3]OTf and [5][OTf]2 suggest that polarization by the CO group results in significant contributions from the alkynyl-allenylidene or alkynyl-carbyne mesomers, respectively. Reaction of 2 in refluxing MeOH containing [NH4]PF6 results in partial methanolysis to give Ru{C≡CC(O)CH═CH(OMe)}(dppe)Cp* (6). Knövenagel condensation of 2 with CH₂(CN)₂ affords {[Ru(dppe)Cp*]C≡C}₂C═C(CN) ₂ (7). The related asymmetric complex {Cp*(dppe)Ru}C≡C[C═C(CN)₂]C≡CC≡C{Ru(dppe)Cp*} (8) was obtained from the reaction between Ru{C≡CC(CN)═C(CN)₂}(dppe)Cp* and lithiated Ru(C≡CC≡CH)(dppe)Cp*. Single-crystal structural determinations of 2, [3]OTf, [5][OTf]₂, 6, 7, and 8 are reported, together with a supporting computational study of relevant electronic structures.

text: Some Ruthenium Derivatives of Penta-1,4-diyn-3-one The reaction between Ru(C≡CH)(dppe)Cp* (1) and oxalyl chloride affords ({Ru(dppe)Cp*}C≡C)₂CO (2) in 72% yield. Methylation (MeOTf) of 2 occurs first on the carbonyl oxygen, affording [({Ru(dppe)Cp*}C≡C)2C(OMe)]OTf ([3]OTf). A second methylation of [3]⁺ on the alkynyl Cβ proceeds slowly, affording [{Cp*(dppe)Ru}CCMeC(OMe)CC{Ru(dppe)Cp*}][OTf]₂ ([4][OTf]₂), whereas protonation of [3]+ occurs readily to give crystallographically characterized [{Cp*(dppe)Ru}CCHC(OMe)CC{Ru(dppe)Cp*}][OTf]₂ ([5][OTf]₂). The molecular structures of [3]OTf and [5][OTf]2 suggest that polarization by the CO group results in significant contributions from the alkynyl-allenylidene or alkynyl-carbyne mesomers, respectively. Reaction of 2 in refluxing MeOH containing [NH4]PF6 results in partial methanolysis to give Ru{C≡CC(O)CH═CH(OMe)}(dppe)Cp* (6). Knövenagel condensation of 2 with CH₂(CN)₂ affords {[Ru(dppe)Cp*]C≡C}₂C═C(CN) ₂ (7). The related asymmetric complex {Cp*(dppe)Ru}C≡C[C═C(CN)₂]C≡CC≡C{Ru(dppe)Cp*} (8) was obtained from the reaction between Ru{C≡CC(CN)═C(CN)₂}(dppe)Cp* and lithiated Ru(C≡CC≡CH)(dppe)Cp*. Single-crystal structural determinations of 2, [3]OTf, [5][OTf]₂, 6, 7, and 8 are reported, together with a supporting computational study of relevant electronic structures.

year: 2013

title: Bridging language barriers in statistics for Year-12 Pasifika students: A collaborative study

authors: Sharma, Sashi

abstract: This paper focuses on the use of home languages as a resource for Pasifika students who are learning about statistical methods. It is acknowledged that there are connections between language use and mathematics in mathematics learning and teaching, and the potential challenges this issue can pose have been investigated by researchers. Yet how the challenges of the use of home language versus teaching language might be overcome in statistics classrooms, where language is even more important as a medium of instruction, has received very little scrutiny. This article reports on research carried out in three New Zealand largely Pasifika dominated Year-12 classes. Data was collected from audio recordings of student group discussions and teacher reflections while students were carrying out an investigation of existing datasets. Findings from the teacher reflection aspect of the study indicate that teachers can struggle with how to use home language and real-life contexts to maximise learning in their classroom. Some strategies to incorporate students home language in their learning worked better than others. However, more in-depth research is needed to explore language issues and the barriers they might present in statistics education.

text: Bridging language barriers in statistics for Year-12 Pasifika students: A collaborative study This paper focuses on the use of home languages as a resource for Pasifika students who are learning about statistical methods. It is acknowledged that there are connections between language use and mathematics in mathematics learning and teaching, and the potential challenges this issue can pose have been investigated by researchers. Yet how the challenges of the use of home language versus teaching language might be overcome in statistics classrooms, where language is even more important as a medium of instruction, has received very little scrutiny. This article reports on research carried out in three New Zealand largely Pasifika dominated Year-12 classes. Data was collected from audio recordings of student group discussions and teacher reflections while students were carrying out an investigation of existing datasets. Findings from the teacher reflection aspect of the study indicate that teachers can struggle with how to use home language and real-life contexts to maximise learning in their classroom. Some strategies to incorporate students home language in their learning worked better than others. However, more in-depth research is needed to explore language issues and the barriers they might present in statistics education.

year: 2018

title: Evaluation of the Whānau Ora Wellbeing Service of Te Whakaruruhau: Final report

authors: Robertson, Neville

subjects: whānau ora

abstract: Domestic violence and child abuse represent significant threats to whānau ora. Conversely, the weakening or loss of whānau ties can increase the vulnerability of whānau members to domestic violence and child abuse. Thus enhancing whānau ora in the context of domestic violence and child abuse is both a high priority and a significant challenge.

Te Whakaruruhau Māori Women’s Refuge has been providing safe housing, support and advocacy to women and children for over two decades and has become a key agency in family violence networks in Kirikiriroa. The development of the Whānau Ora Wellbeing Service, the focus of this evaluation, was a logical extension of Refuge services.

The Māori and Psychology Research Unit was commissioned in mid‐2011 to conduct this evaluation. It is based on ten case studies of clients in the programme, interviews with Te Whakaruruhau staff and key informants in allied agencies, and participant‐observation of Refuge activities. The case studies provide insights into the lived experience of women dealing with violence, their attempts to protect themselves and their children, and their experiences of – and reflections upon – the Whānau Ora Wellbeing programme.

text: Evaluation of the Whānau Ora Wellbeing Service of Te Whakaruruhau: Final report Domestic violence and child abuse represent significant threats to whānau ora. Conversely, the weakening or loss of whānau ties can increase the vulnerability of whānau members to domestic violence and child abuse. Thus enhancing whānau ora in the context of domestic violence and child abuse is both a high priority and a significant challenge.

Te Whakaruruhau Māori Women’s Refuge has been providing safe housing, support and advocacy to women and children for over two decades and has become a key agency in family violence networks in Kirikiriroa. The development of the Whānau Ora Wellbeing Service, the focus of this evaluation, was a logical extension of Refuge services.

The Māori and Psychology Research Unit was commissioned in mid‐2011 to conduct this evaluation. It is based on ten case studies of clients in the programme, interviews with Te Whakaruruhau staff and key informants in allied agencies, and participant‐observation of Refuge activities. The case studies provide insights into the lived experience of women dealing with violence, their attempts to protect themselves and their children, and their experiences of – and reflections upon – the Whānau Ora Wellbeing programme.

year: 2013-07-20