title: Exploring the Lewis basicity of the metalloligand [Pt₂(μ-Se)₂(PPh₃)₄] on metal substrates by electrospray mass spectrometry. Synthesis, characterization and structural studies of new platinum selenido phosphine complexes containing the {Pt₂Se₂} core

authors: Yeo, Jeremy S.L.

subjects: chemistry

abstract: Electrospray Mass Spectrometry (ESMS) has been used as a tool to probe the reactivity of the metalloligand [Pt₂(μ-Se)₂(PPh₃)₄] with metal substrates, which lead to the formation of charged coordination complexes via loss of halides or other labile ligands. Among the numerous metal substrates used in the displacement reactions are Au(anpy)Cl₂ (anpy = cyclometallated 2-anilinopyridyl), HgPhCl and Pb(NO₃)₂. Acid titration on the Lewis basic metalloligand leads to the identification and isolation of the doubly-protonated species, [Pt₂(μ-SeH)₂(PPh₃)₄]²⁺, whose sulfide analogue cannot be isolated. A three-step strategy is employed in the use of ESMS as a probe: (i) preliminary screening of the metalloligand with an array of acidic main group and transition group metal compounds, (ii) identification of potentially stable and isolable products formed in situ based on ion distribution and simulated isotope patterns and (iii) promising reactions are repeated on a laboratory scale, and target products are isolated and characterized. X-Ray diffraction studies have been performed on single crystals of [Pt₂(μ-SeH)₂(PPh₃)₄][ClO₄]₂, [Pt₂(μ₃-Se)₂(PPh₃)₄(CdCl₂)] and {Pt₂(μ₃-Se)₂(PPh₃)₄[Pb(NO₃)]}{NO₃}. These results suggested that in general a parallel chemistry can be developed on the intermetallic selenides as on the sulfides. However, there are chemical and structural differences which are highlighted in this paper.

text: Exploring the Lewis basicity of the metalloligand [Pt₂(μ-Se)₂(PPh₃)₄] on metal substrates by electrospray mass spectrometry. Synthesis, characterization and structural studies of new platinum selenido phosphine complexes containing the {Pt₂Se₂} core Electrospray Mass Spectrometry (ESMS) has been used as a tool to probe the reactivity of the metalloligand [Pt₂(μ-Se)₂(PPh₃)₄] with metal substrates, which lead to the formation of charged coordination complexes via loss of halides or other labile ligands. Among the numerous metal substrates used in the displacement reactions are Au(anpy)Cl₂ (anpy = cyclometallated 2-anilinopyridyl), HgPhCl and Pb(NO₃)₂. Acid titration on the Lewis basic metalloligand leads to the identification and isolation of the doubly-protonated species, [Pt₂(μ-SeH)₂(PPh₃)₄]²⁺, whose sulfide analogue cannot be isolated. A three-step strategy is employed in the use of ESMS as a probe: (i) preliminary screening of the metalloligand with an array of acidic main group and transition group metal compounds, (ii) identification of potentially stable and isolable products formed in situ based on ion distribution and simulated isotope patterns and (iii) promising reactions are repeated on a laboratory scale, and target products are isolated and characterized. X-Ray diffraction studies have been performed on single crystals of [Pt₂(μ-SeH)₂(PPh₃)₄][ClO₄]₂, [Pt₂(μ₃-Se)₂(PPh₃)₄(CdCl₂)] and {Pt₂(μ₃-Se)₂(PPh₃)₄[Pb(NO₃)]}{NO₃}. These results suggested that in general a parallel chemistry can be developed on the intermetallic selenides as on the sulfides. However, there are chemical and structural differences which are highlighted in this paper.

year: 2002

title: Dibia's world: Life on an early sugar plantation

authors: Jennings, William

abstract: A 45-minute online presentation of my research into the early phase of industrial slavery, followed by a 35-minute discussion and Q&A session. The presentation was to members of the Centre for the Study of International Slavery based at the University of Liverpool. The choice of date, 25 March, was important as it is the International Day of Remembrance of the Victims of Slavery and the Transatlantic Slave Trade.

text: Dibia's world: Life on an early sugar plantation A 45-minute online presentation of my research into the early phase of industrial slavery, followed by a 35-minute discussion and Q&A session. The presentation was to members of the Centre for the Study of International Slavery based at the University of Liverpool. The choice of date, 25 March, was important as it is the International Day of Remembrance of the Victims of Slavery and the Transatlantic Slave Trade.

year: 2025-03-25

title: Ngā tohu o te taiao: Observing signs of the natural world to identify seastar over-abundance as a detriment to shellfish survival in Ōhiwa Harbour, Aotearoa New Zealand

authors: Paul-Burke, Kura

subjects: Tohu

abstract: Māori understandings and experiences of the natural world encompass not only what is known but how it is known, and the intergenerational connectedness of that knowledge with the environments from which it is derived. Ngā tohu o te taiao (hereafter ‘tohu’), or the cultural and environmental signs and indicators of the natural world, are widely used by kaitiaki or local practitioners to identify trends or changes in the state or health of marine taonga (culturally important) species and their associated environments (Paul-Burke, 2017). Māori worldviews position humans within nature and focus on ways in which cultural understandings and intergenerational connections between people and their bio-physical contexts assist in the retention and protection of biodiversity and ecologically sustainable ecosystems (Lyver et al., 2016). Tohu are a fundamental expression of kaitiakitanga or active guardianship and are based on the primal instinct of survival and recognising that in order to survive one must pay attention to the natural signs and signals thoughtfully, so as to manage our mahinga kai (food harvesting area) and ourselves into the future (Paul-Burke et al., 2020). This article considers the example of the over-abundant eleven-armed seastar (pātangaroa, Coscinasterias muricata; hereafter ‘seastar’) predating on culturally and ecologically important shellfish populations in a traditional mahinga kai of Ōhiwa Harbour in the Bay of Plenty region of Aotearoa/New Zealand. The over-abundance of seastars was considered a contemporary tohu of a degrading harbour. It was deemed imperative by iwi (tribe) members that a trial using quantitative methods to investigate predation pressure of seastars on the green-lipped mussel (kuku or kūtai, Perna canaliculus) population be conducted in the harbour. Between September 2018 and February 2019 field trials were undertaken that prioritised mātauranga Māori (Māori knowledge) alongside marine science to assist with a better understanding of the degrading harbour. It was hoped that the research would help and promote recovery, in particular but not limited to, the once abundant but now severely reduced mussel reefs in the soft-mud-bottomed harbour.

text: Ngā tohu o te taiao: Observing signs of the natural world to identify seastar over-abundance as a detriment to shellfish survival in Ōhiwa Harbour, Aotearoa New Zealand Māori understandings and experiences of the natural world encompass not only what is known but how it is known, and the intergenerational connectedness of that knowledge with the environments from which it is derived. Ngā tohu o te taiao (hereafter ‘tohu’), or the cultural and environmental signs and indicators of the natural world, are widely used by kaitiaki or local practitioners to identify trends or changes in the state or health of marine taonga (culturally important) species and their associated environments (Paul-Burke, 2017). Māori worldviews position humans within nature and focus on ways in which cultural understandings and intergenerational connections between people and their bio-physical contexts assist in the retention and protection of biodiversity and ecologically sustainable ecosystems (Lyver et al., 2016). Tohu are a fundamental expression of kaitiakitanga or active guardianship and are based on the primal instinct of survival and recognising that in order to survive one must pay attention to the natural signs and signals thoughtfully, so as to manage our mahinga kai (food harvesting area) and ourselves into the future (Paul-Burke et al., 2020). This article considers the example of the over-abundant eleven-armed seastar (pātangaroa, Coscinasterias muricata; hereafter ‘seastar’) predating on culturally and ecologically important shellfish populations in a traditional mahinga kai of Ōhiwa Harbour in the Bay of Plenty region of Aotearoa/New Zealand. The over-abundance of seastars was considered a contemporary tohu of a degrading harbour. It was deemed imperative by iwi (tribe) members that a trial using quantitative methods to investigate predation pressure of seastars on the green-lipped mussel (kuku or kūtai, Perna canaliculus) population be conducted in the harbour. Between September 2018 and February 2019 field trials were undertaken that prioritised mātauranga Māori (Māori knowledge) alongside marine science to assist with a better understanding of the degrading harbour. It was hoped that the research would help and promote recovery, in particular but not limited to, the once abundant but now severely reduced mussel reefs in the soft-mud-bottomed harbour.

year: 2022-03-28