title: Moderating the nucleophilicity of the sulfide ligands in the dinuclear {Pt₂S₂} metalloligand system using triphenylarsine

authors: Jeram, Sunita

subjects: Arsine ligands

abstract: Reaction of cis-[PtCl₂(AsPh₃)₂] with excess sodium sulfide in benzene gave the triphenylarsine analogue of the well-known metalloligand [Pt₂(μ-S)₂(PPh₃)₄] as an orange solid.The compound was characterised by detailed mass spectrometry studies, and by conversion to various alkylated and metallated derivatives.The sulfide ligands in [Pt₂(μ-S)₂(AsPh₃)₄] are less basic than the triphenylphosphine analogue, and the complex gives a relatively weak [M+H]⁺ ion in the positive-ion electrospray (ESI) mass spectrum, compared with the phosphine analogue.Methylation of an equimolar mixture of [Pt₂(μ-S)₂(PPh₃)₄] and [Pt₂(μ-S)₂(AsPh₃)₄] with MeI gave the species [Pt₂(μ-S)(μ-SMe)(AsPh₃)₄]⁺ and [Pt₂(μ-SMe)₂(PPh₃)₃I]⁺, indicating a reduced tendency for the sulfide of [Pt₂(μ-S)(μ-SMe)(AsPh₃)₄]⁺ to undergo alkylation.The lability of the arsine ligands is confirmed by the reaction of an equimolar mixture of [Pt₂(μ-S)₂(PPh₃)₄] and [Pt₂(μ-S)₂(AsPh₃)₄] with n-butyl chloride, giving [Pt₂(μ-S)(μ-SBu)(Eph₃)₄] (E = P, As), which with Me₂SO₄ gave a mixture of [Pt₂(μ-SMe)(μ-SBu)(PPh₃)₄]²⁺ and [Pt₂(μ-SMe)(μ-SBu)(AsPh₃)₃Cl]⁺.Reactivity towards 1,2-dichloroethane follows a similar pattern.The formation and ESI MS detection of mixed phosphine–arsine {Pt₂S₂} species of the type[Pt₂(μ-S)₂(AsPh₃)n(PPh₃)4−n] is also discussed. Coordination chemistry of [Pt₂(μ-S)₂(AsPh₃)₄] towards a range of metal-chloride substrates, forming sulfide-bridged trinuclear aggregates, has also been probed using ESI MS, and found to be similar to the phosphine analogue. The X-ray crystal structure of [Pt₂(μ-S)₂(AsPh₃)₄Pt(cod)](PF₆)₂ (cod = 1,5-cyclo-octadiene) has been determined for comparison with the (previously reported) triphenylphosphine analogue. ESI MS is a powerful tool in exploring the chemistry of this system; in some cases the derivatising agent p-bromobenzyl bromide is used to convert sparingly soluble and/or poorly ionising {Pt₂S₂} species into soluble, charged derivatives for MS analysis.

text: Moderating the nucleophilicity of the sulfide ligands in the dinuclear {Pt₂S₂} metalloligand system using triphenylarsine Reaction of cis-[PtCl₂(AsPh₃)₂] with excess sodium sulfide in benzene gave the triphenylarsine analogue of the well-known metalloligand [Pt₂(μ-S)₂(PPh₃)₄] as an orange solid.The compound was characterised by detailed mass spectrometry studies, and by conversion to various alkylated and metallated derivatives.The sulfide ligands in [Pt₂(μ-S)₂(AsPh₃)₄] are less basic than the triphenylphosphine analogue, and the complex gives a relatively weak [M+H]⁺ ion in the positive-ion electrospray (ESI) mass spectrum, compared with the phosphine analogue.Methylation of an equimolar mixture of [Pt₂(μ-S)₂(PPh₃)₄] and [Pt₂(μ-S)₂(AsPh₃)₄] with MeI gave the species [Pt₂(μ-S)(μ-SMe)(AsPh₃)₄]⁺ and [Pt₂(μ-SMe)₂(PPh₃)₃I]⁺, indicating a reduced tendency for the sulfide of [Pt₂(μ-S)(μ-SMe)(AsPh₃)₄]⁺ to undergo alkylation.The lability of the arsine ligands is confirmed by the reaction of an equimolar mixture of [Pt₂(μ-S)₂(PPh₃)₄] and [Pt₂(μ-S)₂(AsPh₃)₄] with n-butyl chloride, giving [Pt₂(μ-S)(μ-SBu)(Eph₃)₄] (E = P, As), which with Me₂SO₄ gave a mixture of [Pt₂(μ-SMe)(μ-SBu)(PPh₃)₄]²⁺ and [Pt₂(μ-SMe)(μ-SBu)(AsPh₃)₃Cl]⁺.Reactivity towards 1,2-dichloroethane follows a similar pattern.The formation and ESI MS detection of mixed phosphine–arsine {Pt₂S₂} species of the type[Pt₂(μ-S)₂(AsPh₃)n(PPh₃)4−n] is also discussed. Coordination chemistry of [Pt₂(μ-S)₂(AsPh₃)₄] towards a range of metal-chloride substrates, forming sulfide-bridged trinuclear aggregates, has also been probed using ESI MS, and found to be similar to the phosphine analogue. The X-ray crystal structure of [Pt₂(μ-S)₂(AsPh₃)₄Pt(cod)](PF₆)₂ (cod = 1,5-cyclo-octadiene) has been determined for comparison with the (previously reported) triphenylphosphine analogue. ESI MS is a powerful tool in exploring the chemistry of this system; in some cases the derivatising agent p-bromobenzyl bromide is used to convert sparingly soluble and/or poorly ionising {Pt₂S₂} species into soluble, charged derivatives for MS analysis.

year: 2006-06-01

title: Counselling children in Years 1-8: Scoping primary school counselling in Aotearoa New Zealand

authors: Flanagan, Paul G.

abstract: In July 2020, due to the effects of Covid-19, the Government made funding available for counselling in primary schools. Counselling in Primary Schools is not common in Aotearoa. Where this exists it is usually through community organisations as a funded service (e.g. by MSD or ACC for specific projects such as family violence prevention) or MoH (Mana Ake). There are a few schools that employ counsellors. This study explores examples of where and how counselling has been offered in primary schools. It documents that experience and provides data to argue for further expansion of counselling services in primary schools.

text: Counselling children in Years 1-8: Scoping primary school counselling in Aotearoa New Zealand In July 2020, due to the effects of Covid-19, the Government made funding available for counselling in primary schools. Counselling in Primary Schools is not common in Aotearoa. Where this exists it is usually through community organisations as a funded service (e.g. by MSD or ACC for specific projects such as family violence prevention) or MoH (Mana Ake). There are a few schools that employ counsellors. This study explores examples of where and how counselling has been offered in primary schools. It documents that experience and provides data to argue for further expansion of counselling services in primary schools.

year: 2021

title: An external evaluation of Phat Pak process and structure: Volume 1: Evaluation report

authors: Masters-Awatere, Bridgette

subjects: psychology

abstract: An evaluation was conducted by the 510 Evaluation Research Group 2007 after receiving a request from the Phat Pak Governance Group (PPGG). The evaluation focused on four areas identified in the Phat Pak service specification plan attached to it’s Ministry of Health contract (Youth participation, Communication Strategies, Decision making Processes and Skills Development). Our intention of evaluating the Phat Pak Programme has been to, through feedback from a range of participants, gauge the extent that the programme objectives (such as those highlighted in the contract are being met. More specifically, the function of the evaluation has been to help identify specific areas that are working well and those areas that need further development. It is our intention that the evaluation will provide both short and long-term direction with added insight towards increasing participation and enhancing health outcomes for youth and the wider community of the Waikato region.

text: An external evaluation of Phat Pak process and structure: Volume 1: Evaluation report An evaluation was conducted by the 510 Evaluation Research Group 2007 after receiving a request from the Phat Pak Governance Group (PPGG). The evaluation focused on four areas identified in the Phat Pak service specification plan attached to it’s Ministry of Health contract (Youth participation, Communication Strategies, Decision making Processes and Skills Development). Our intention of evaluating the Phat Pak Programme has been to, through feedback from a range of participants, gauge the extent that the programme objectives (such as those highlighted in the contract are being met. More specifically, the function of the evaluation has been to help identify specific areas that are working well and those areas that need further development. It is our intention that the evaluation will provide both short and long-term direction with added insight towards increasing participation and enhancing health outcomes for youth and the wider community of the Waikato region.

year: 2007-12