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: An integrated theory of sexual recidivism

authors: Thakker, Jo

subjects: sex offenders

abstract: Over the last twenty years, theories of sexual offending have received a great deal of attention in the literature and there have been a number of important developments. While some theories have focused on the identification of specific causal factors, others have brought together a range of factors in the form of integrated models. Theoreticians who work in this field share the common goal of explaining this highly problematic behaviour so that appropriate interventions can be developed. However, it is interesting to note that, to date, the theoretical research has looked primarily at sexual offending per se, rather than sexual reoffending; thus, there appears to be a gap in the literature. This article seeks to lay out a framework for filling this gap by bringing together two typically disparate bodies of literature; namely, the theories of sexual offending and the risk factors for sexual reoffending.

text: An integrated theory of sexual recidivism Over the last twenty years, theories of sexual offending have received a great deal of attention in the literature and there have been a number of important developments. While some theories have focused on the identification of specific causal factors, others have brought together a range of factors in the form of integrated models. Theoreticians who work in this field share the common goal of explaining this highly problematic behaviour so that appropriate interventions can be developed. However, it is interesting to note that, to date, the theoretical research has looked primarily at sexual offending per se, rather than sexual reoffending; thus, there appears to be a gap in the literature. This article seeks to lay out a framework for filling this gap by bringing together two typically disparate bodies of literature; namely, the theories of sexual offending and the risk factors for sexual reoffending.

year: 2012

title: Mental health and wellbeing for young people from intersectional identity groups: Inequity for Māori, Pacific, Rainbow young people, and those with a disabling condition

authors: Roy, Rituparna

subjects: Māori

abstract: ‘Intersectionality’ describes the converging effects of ethnicity, gender, sexuality, disability, and other social group characteristics that influence life experiences. We draw on a representative study of year 9-13 students in Tai Tokerau, Tāmaki Makaurau, and Waikato (Youth19) to explore differences in mental health and wellbeing outcomes for young people from a selection of intersectional identities (Māori, Pasifika, Rainbow, and young people with a Disabling Condition). We found a pervasive pattern of inequity for young people who have intersectional identities compared to those from the majority groups (i.e. Pākehā, non-disabled, cis-heterosexual youth). Intersectional youth had higher levels of inequity and faced a greater array of inequities. There was evidence of an additive effect for some indicators. Thematic analysis of open-text survey responses found the need for positive inclusive environments, and support for all young people, including those at the intersections of identity. Drawing on the findings, we offered several systemslevel policy recommendations, including strategies to improve inclusiveness and reduce discrimination.

text: Mental health and wellbeing for young people from intersectional identity groups: Inequity for Māori, Pacific, Rainbow young people, and those with a disabling condition ‘Intersectionality’ describes the converging effects of ethnicity, gender, sexuality, disability, and other social group characteristics that influence life experiences. We draw on a representative study of year 9-13 students in Tai Tokerau, Tāmaki Makaurau, and Waikato (Youth19) to explore differences in mental health and wellbeing outcomes for young people from a selection of intersectional identities (Māori, Pasifika, Rainbow, and young people with a Disabling Condition). We found a pervasive pattern of inequity for young people who have intersectional identities compared to those from the majority groups (i.e. Pākehā, non-disabled, cis-heterosexual youth). Intersectional youth had higher levels of inequity and faced a greater array of inequities. There was evidence of an additive effect for some indicators. Thematic analysis of open-text survey responses found the need for positive inclusive environments, and support for all young people, including those at the intersections of identity. Drawing on the findings, we offered several systemslevel policy recommendations, including strategies to improve inclusiveness and reduce discrimination.

year: 2023