title: Tuning the sulfur–heterometal interaction in organolead(IV) complexes of [Pt₂(μ-S)₂(PPh₃)₄]

authors: Pham, Kristina

subjects: Platinum complexes

abstract: Reactions of [Pt₂(μ-S)₂(PPh₃)₄] with Ph₃PbCl, Ph₂PbI₂, Ph₂PbBr₂ and Me₃PbOAc result in the formation of bright yellow to orange solutions containing the cations [Pt₂(μ-S)₂(PPh₃)₄PbR₃]⁺ (R₃ = Ph₃, Ph₂I, Ph₂Br, Me₃) isolated as PF₆⁻ or BPh₄⁻ salts. In the case of the Me₃Pb and Et₃Pb systems, a prolonged reaction time results in formation of the alkylated species [Pt₂(μ-S)(μ-SR)(PPh₃)₄]⁺ (R = Me, Et). X-ray structure determinations on [Pt₂(μ-S)₂(PPh₃)₄PbMe₃]PF₆ and [Pt₂(μ-S)₂(PPh₃)₄PbPh₂I]PF₆ have been carried out, revealing different coordination modes. In the Me₃Pb complex, the (four-coordinate) lead atom binds to a single sulfur atom, while in the Ph₂PbI adduct coordination of both sulfurs results in a five-coordinate lead centre. These differences are related to the electron density on the lead centre, and indicate that the interaction of the heterometal centre with the {Pt₂S₂} metalloligand core can be tuned by variation of the heteroatom substituents. The species [Pt₂(μ-S)₂(PPh₃)₄PbR₃]⁺ display differing fragmentation pathways in their ESI mass spectra, following initial loss of PPh₃ in all cases; for R = Ph, loss of PbPh₂ occurs, yielding [Pt₂(μ-S)₂(PPh₃)₃Ph]⁺, while for R = Me, reductive elimination of ethane gives [Pt₂(μ-S)₂(PPh₃)₃PbMe]⁺, which is followed by loss of CH₄.

text: Tuning the sulfur–heterometal interaction in organolead(IV) complexes of [Pt₂(μ-S)₂(PPh₃)₄] Reactions of [Pt₂(μ-S)₂(PPh₃)₄] with Ph₃PbCl, Ph₂PbI₂, Ph₂PbBr₂ and Me₃PbOAc result in the formation of bright yellow to orange solutions containing the cations [Pt₂(μ-S)₂(PPh₃)₄PbR₃]⁺ (R₃ = Ph₃, Ph₂I, Ph₂Br, Me₃) isolated as PF₆⁻ or BPh₄⁻ salts. In the case of the Me₃Pb and Et₃Pb systems, a prolonged reaction time results in formation of the alkylated species [Pt₂(μ-S)(μ-SR)(PPh₃)₄]⁺ (R = Me, Et). X-ray structure determinations on [Pt₂(μ-S)₂(PPh₃)₄PbMe₃]PF₆ and [Pt₂(μ-S)₂(PPh₃)₄PbPh₂I]PF₆ have been carried out, revealing different coordination modes. In the Me₃Pb complex, the (four-coordinate) lead atom binds to a single sulfur atom, while in the Ph₂PbI adduct coordination of both sulfurs results in a five-coordinate lead centre. These differences are related to the electron density on the lead centre, and indicate that the interaction of the heterometal centre with the {Pt₂S₂} metalloligand core can be tuned by variation of the heteroatom substituents. The species [Pt₂(μ-S)₂(PPh₃)₄PbR₃]⁺ display differing fragmentation pathways in their ESI mass spectra, following initial loss of PPh₃ in all cases; for R = Ph, loss of PbPh₂ occurs, yielding [Pt₂(μ-S)₂(PPh₃)₃Ph]⁺, while for R = Me, reductive elimination of ethane gives [Pt₂(μ-S)₂(PPh₃)₃PbMe]⁺, which is followed by loss of CH₄.

year: 2007

title: Nutritionism and the construction of 'poor choices' in families facing food insecurity

authors: Graham, Rebekah Sarah

subjects: Social Sciences

abstract: The dominant research approach to both food insecurity and charitable meal provision is nutritionistic, deficit-orientated and ignores wider socio-economic issues. This reinforces existing power dynamics and overlooks the agency of people living food-insecure lives. We critique this dominant approach and draw on the everyday experiences of families facing food insecurity to ground an alternative approach that emphasises food as a social determinant of health.

text: Nutritionism and the construction of 'poor choices' in families facing food insecurity The dominant research approach to both food insecurity and charitable meal provision is nutritionistic, deficit-orientated and ignores wider socio-economic issues. This reinforces existing power dynamics and overlooks the agency of people living food-insecure lives. We critique this dominant approach and draw on the everyday experiences of families facing food insecurity to ground an alternative approach that emphasises food as a social determinant of health.

year: 2018

title: Science-practice roadshow 1: Summary perspectives from centralised entities and agencies

authors: Serrao-Neumann, Silvia

abstract: Flooding is Aotearoa-New Zealand’s most frequent natural hazard, regularly damaging buildings and infrastructure networks, and causing months of disruption to communities and businesses (Hutchings et al. 2019). Also, floods have indirect, cascading, and more intangible impacts (Lawrence, Blackett, and Cradock-Henry 2020), such as the withdrawal of future investment or the emotional stress of recovery. flood risk is predicted to rise quickly due to the combination of climate change and rapid urban intensification (Ministry for the Environment and The Flood Risk Management and River Control Review Steering Group 2008). 

Currently, there is no consistent approach to accurately determine flood risk on a national scale, nor how this may be changing as the climate warms. Instead, flooding risk assessments are done for individual catchments or locations, with the goal of managing and mitigating on the local scale. Local and regional governments vary widely in their capability and capacity to undertake this work (Ford, Berrang-Ford, and Berrang Ford 2011) and, thus, significant differences in data availability and modelling approaches mean that integration of results to gain a pan-region or nationwide picture has not been possible. 

The ‘Mā te haumaru ō nga puna wai ō Rākaihautū ka ora mo ake tonu: Increasing flood resilience across Aotearoa’ research develop a detailed nationwide model that could inform strategic and co-ordinated nationwide decision-making and regulations to support improved resilience to flood risk across the country. Utilising new methods and advances in computer processing and automation, the programme is developing a dynamic risk modelling framework that will assess flood hazard for every catchment in the country and under differing climate scenarios. The model will account for the risks to both built infrastructure and communities so that a fuller understanding of societal costs and impacts can be established. The model’s utility for supporting decision-making will be investigated using an initial set of scenarios for environmental planning, policy settings and infrastructure investment options. Two overarching themes across all of the research - Mtauranga Mori and Uncertainty – are designed to utilise the diverse knowledge systems available to develop tools that are relevant for communities throughout Aotearoa-New Zealand, and to take into account and communicate more clearly flood risks. 

Improved resilience to flooding across Aotearoa-New Zealand is a key outcome sought by the research programme, however it cannot be achieved by research alone. Instead, knowledge and information developed within the programme must be utilised by practitioners in their work to assist communities to plan for, manage, mitigate and avoid flood risks. New knowledge from the programme must be incorporated by practitioners into further tools, policy and decision-making frameworks. This knowledge translation however is not a straight forward process (Dilling and Lemos 2011). Cultural, behavioural and cognitive differences between those who produce and those who utilise knowledge mean that research outputs may not fit the requirements of their intended users, and thus, uptake of research outputs may be compromised. Conversely, strong engagement of knowledge users in the knowledge production process is known to increase the likelihood, and impact, of knowledge implementation. 

Stakeholders are key members of the programme’s research team, representing views across central and local government, engineering, planning consultancies, emergency management, insurance and banking industries, and Te Rūnanga o Wairewa (Banks Peninsula). To broaden the range of stakeholder perspectives, and to facilitate relationships across the programme, we have established a boundary organisation – Te W Te W . Boundary organisations (Guston 2001; Kirchhoff, Esselman, and Brown 2015) are forums that bridge between the two relatively different social worlds of knowledge producers (researchers/scientists) and users (practitioners/policy makers). These forums create and sustain legitimate space and collaboration for knowledge/information to be co-designed, co-produced and co-disseminated (Serrao-Neumann, Di Giulio, and Low Choy 2020). Within our programme, Te W Te W is responsible for organising and facilitating communication and collaboration activities – events (Science-Practice oadshows), communications channels such as an electronic newsletter and website, and learning opportunities. Through this organisation, we are fostering trust, legitimacy and capacity for information use so that our research results will be usable, useful, and used. 

This report summarises the discussion and perspectives shared at the first Science-Practice Roadshow held in October 2021.

text: Science-practice roadshow 1: Summary perspectives from centralised entities and agencies Flooding is Aotearoa-New Zealand’s most frequent natural hazard, regularly damaging buildings and infrastructure networks, and causing months of disruption to communities and businesses (Hutchings et al. 2019). Also, floods have indirect, cascading, and more intangible impacts (Lawrence, Blackett, and Cradock-Henry 2020), such as the withdrawal of future investment or the emotional stress of recovery. flood risk is predicted to rise quickly due to the combination of climate change and rapid urban intensification (Ministry for the Environment and The Flood Risk Management and River Control Review Steering Group 2008). 

Currently, there is no consistent approach to accurately determine flood risk on a national scale, nor how this may be changing as the climate warms. Instead, flooding risk assessments are done for individual catchments or locations, with the goal of managing and mitigating on the local scale. Local and regional governments vary widely in their capability and capacity to undertake this work (Ford, Berrang-Ford, and Berrang Ford 2011) and, thus, significant differences in data availability and modelling approaches mean that integration of results to gain a pan-region or nationwide picture has not been possible. 

The ‘Mā te haumaru ō nga puna wai ō Rākaihautū ka ora mo ake tonu: Increasing flood resilience across Aotearoa’ research develop a detailed nationwide model that could inform strategic and co-ordinated nationwide decision-making and regulations to support improved resilience to flood risk across the country. Utilising new methods and advances in computer processing and automation, the programme is developing a dynamic risk modelling framework that will assess flood hazard for every catchment in the country and under differing climate scenarios. The model will account for the risks to both built infrastructure and communities so that a fuller understanding of societal costs and impacts can be established. The model’s utility for supporting decision-making will be investigated using an initial set of scenarios for environmental planning, policy settings and infrastructure investment options. Two overarching themes across all of the research - Mtauranga Mori and Uncertainty – are designed to utilise the diverse knowledge systems available to develop tools that are relevant for communities throughout Aotearoa-New Zealand, and to take into account and communicate more clearly flood risks. 

Improved resilience to flooding across Aotearoa-New Zealand is a key outcome sought by the research programme, however it cannot be achieved by research alone. Instead, knowledge and information developed within the programme must be utilised by practitioners in their work to assist communities to plan for, manage, mitigate and avoid flood risks. New knowledge from the programme must be incorporated by practitioners into further tools, policy and decision-making frameworks. This knowledge translation however is not a straight forward process (Dilling and Lemos 2011). Cultural, behavioural and cognitive differences between those who produce and those who utilise knowledge mean that research outputs may not fit the requirements of their intended users, and thus, uptake of research outputs may be compromised. Conversely, strong engagement of knowledge users in the knowledge production process is known to increase the likelihood, and impact, of knowledge implementation. 

Stakeholders are key members of the programme’s research team, representing views across central and local government, engineering, planning consultancies, emergency management, insurance and banking industries, and Te Rūnanga o Wairewa (Banks Peninsula). To broaden the range of stakeholder perspectives, and to facilitate relationships across the programme, we have established a boundary organisation – Te W Te W . Boundary organisations (Guston 2001; Kirchhoff, Esselman, and Brown 2015) are forums that bridge between the two relatively different social worlds of knowledge producers (researchers/scientists) and users (practitioners/policy makers). These forums create and sustain legitimate space and collaboration for knowledge/information to be co-designed, co-produced and co-disseminated (Serrao-Neumann, Di Giulio, and Low Choy 2020). Within our programme, Te W Te W is responsible for organising and facilitating communication and collaboration activities – events (Science-Practice oadshows), communications channels such as an electronic newsletter and website, and learning opportunities. Through this organisation, we are fostering trust, legitimacy and capacity for information use so that our research results will be usable, useful, and used. 

This report summarises the discussion and perspectives shared at the first Science-Practice Roadshow held in October 2021.

year: 2022-02