Peripherally-metallated porphyrins: meso-n1-porphyrinyl-platinum(II) complexes of 5,15-diaryl- and 5,10,15-triarylporphyrins

Attempted metathesis reactions of peripherally-metallated meso-η1-porphyrinylplatinum(II) complexes such as trans-[PtBr(NiDPP)(PPh3)2] (H2DPP = 5,15-diphenylporphyrin) with organolithium reagents fail due to competitive addition at the porphyrin ring carbon opposite to the metal substituent. This reaction can be prevented by using 5,10,15-triarylporphyrins, e.g. 5,10,15-triphenylporphyrin (H2TrPP) and 5-phenyl-10,20-bis(3’,5’-di-t-butylphenyl)porphyrin (H2DAPP) as substrates. These triarylporphyrins are readily prepared using the method of Senge and co-workers by addition of phenyllithium to the appropriate 5,15-diarylporphyrins, followed by aqueous protolysis and oxidation. They are convenient, soluble building blocks for selective substitutions and subsequent transformations at the remaining free meso carbon. The sequence of bromination, optional central metallation and oxidative addition of Pt(0) tris(phosphine) complexes generates the organoplatinum porphyrins in high overall yields. The bromo ligand on the Pt(II) centre can be substituted by alkynyl nucleophiles, including 5-ethynylNiDPP, to form the first examples of meso-η1-porphyrinylplatinum(II) complexes with a second Pt-C bond. The range of porphyrinylplatinum(II) bis(tertiary phosphine) complexes was extended to the triethylphosphine analogues, by oxidative addition of H2TrPPBr to Pt(PEt3)3, and the initially-formed cis adduct is only slowly thermally transformed to trans-[PtBr(H2TrPP)(PEt3)2] 16. The molecular structures of NiDAPP 9b, trans-[Pt(NiDPP)(C2NiDPP)(PPh3)2] 14 and 16 were determined by X-ray crystallography

Human Rights, Refugees, and The Right ‘To Enjoy' Asylum

Increasingly hard-line and restrictive asylum policies and practices of many governments call into question the scope of protections offered by the 1951 Convention relating to the Status of Refugees. Has the focus on the 1951 Convention been to the detriment and subordination of other rights and standards of treatment owed to refugees and asylum-seekers under international human rights law? Which standard applies in the event that there is a clash or inconsistency between the two bodies of law? In analysing the interface between international refugee law and international human rights law, this article looks at the right to family life and the right to work. Through this examination, content and meaning is offered to the almost forgotten component of the right ‘to enjoy' asylum in Article 14(1) of the Universal Declaration of Human Rights 194

World needs leadership and greater political will to combat torture

News in the 2023(1) issue published in 17.03.202

Human Security and the Rights of Refugees: Transcending Territorial and Disciplinary Borders

This Essay examines the concept of human security through the lens of refugee protection. In particular, the author asks whether the concept of human security could add anything to the international protection regime for refugees and asylum seekers under international law. Before international lawyers can reject the notion of human security on the basis of its non-legal, and therefore nonbinding, character, it is necessary to examine the gaps in the existing legal framework, into which policy discourse, including security discourse, may step in as an important player

Human Security and the Rights of Refugees: Transcending Territorial and Disciplinary Borders

This Essay examines the concept of human security through the lens of refugee protection. In particular, the author asks whether the concept of human security could add anything to the international protection regime for refugees and asylum seekers under international law. Before international lawyers can reject the notion of human security on the basis of its non-legal, and therefore nonbinding, character, it is necessary to examine the gaps in the existing legal framework, into which policy discourse, including security discourse, may step in as an important player

An exploration of sarcasm detection in children with Attention Deficit Hyperactivity Disorder

This document is the Accepted Manuscript version of the following article: Amanda K. Ludlow, Eleanor Chadwick, Alice Morey, Rebecca Edwards, and Roberto Gutierrez, ‘An exploration of sarcasm detection in children with Attention Deficit Hyperactivity Disorder’, Journal of Communication Disorders, Vol. 70: 25-34, November 2017. Under embargo. Embargo end date: 31 October 2019. The Version of Record is available at doi: https://doi.org/10.1016/j.jcomdis.2017.10.003.The present research explored the ability of children with ADHD to distinguish between sarcasm and sincerity. Twenty-two children with a clinical diagnosis of ADHD were compared with 22 age and verbal IQ matched typically developing children using the Social Inference–Minimal Test from The Awareness of Social Inference Test (TASIT, McDonald, Flanagan, & Rollins, 2002). This test assesses an individual’s ability to interpret naturalistic social interactions containing sincerity, simple sarcasm and paradoxical sarcasm. Children with ADHD demonstrated specific deficits in comprehending paradoxical sarcasm and they performed significantly less accurately than the typically developing children. While there were no significant differences between the children with ADHD and the typically developing children in their ability to comprehend sarcasm based on the speaker’s intentions and beliefs, the children with ADHD were found to be significantly less accurate when basing their decision on the feelings of the speaker, but also on what the speaker had said. Results are discussed in light of difficulties in their understanding of complex cues of social interactions, and non-literal language being symptomatic of children with a clinical diagnosis of ADHD. The importance of pragmatic language skills in their ability to detect social and emotional information is highlighted.Peer reviewe

Employee Perceptions of Well-Being Programs

Measuring the effectiveness of well-being programs in the workplace is important for optimizing the return on investment and selection of programs that meet organizational objectives. A pilot study was performed to assess employee well-being using the Happiness Mini-Survey and a one-sample pre–post study design intended to quickly allow employees to subjectively rate their well-being before and after participating in various classes as part of a well-being program. The findings demonstrated statistical significance in employee subjective ratings; they reported feeling better emotionally, physically, and mentally after participating in the classes. The employees’ self-rating for stress level also had statistically significant improvement after class participation. These findings are relevant for organizations that intend to offer and evaluate classes with an objective of increasing employee well-being. Recommendations for future studies include the use of more controlled conditions, and a control or comparison group to more robustly test for improvement over time, and the use of qualitative interviews to discover employees’ narratives of how workplace well-being programs can improve work productivity and quality of life

Neurodiversity and Workplace Social Capital Effects on Employee Attitudes and Intentions

Neurodivergent employees have higher turnover rates than their neurotypical peers, andmuch remains unknown about how to improve their workplace experience. The purpose of this quantitative study was to examine the relationships between neurodiversity and workplace social capital on job satisfaction and turnover intent. Social cognitive career theory (SCCT) informed the study design. Working adults (N = 1,243) in the United States recruited using convenience sampling and MTurk participated through an anonymous online survey. Data analysis was conducted using three-way ANOVA and mediation. Significant three-way interactions were found between gender, job classification, and likelihood of having attention deficit hyperactivity disorder (ADHD) on three separate dependent variables: workplace social capital, job satisfaction, and turnover intent. The relationships between neurodiversity symptomology and both job satisfaction and turnover intent were significantly mediated by workplace social capital. These findings add to the body of knowledge in understanding differences between individual workplace experiences relative to worker neurodiversity which can inform HR practice and workplace training and retention initiatives. This study may support social change by encouraging greater consideration of adult ADHD, neurodiversity and workplace social capital within diversity and inclusion (D&I) research and workplace initiatives

Ariel - Volume 3 Number 4

Editors Richard J. Bonanno Robin A. Edwards Associate Editors Steven Ager Tom Williams Lay-out Editor Eugenia Miller Contributing Editors Paul Bialas Robert Breckenridge Lynne Porter David Jacoby Terry Burt Mark Pearlman Michael Leo Mike LeWitt Editors Emeritus Delvyn C. Case, Jr. Paul M. Fernhof