title: Facile syntheses of four-membered aurathietane dioxide [Au–CHR-SO₂-CHR] ring systems, and the first isonitrile insertion reaction into a gold(III)–carbon bond

authors: Henderson, William

subjects: Gold

abstract: The reactions of [Pt₂(μ-S)₂(PPh₃)₄] with excess PbBr₂ or PbI₂ in methanolic suspension result in the formation of the neutral lead(II) halide adducts [Pt₂(μ-S)₂(PPh₃)₄PbX₂] (X = Br, I). The X-ray structure determination of the lead iodide adduct reveals an essentially tetrahedral lead(II) centre, which is a rare coordination geometry for lead(II), which almost invariably is hemidirected, with a stereochemically active lone pair. In contrast, the structure of the PbBr₂ adduct, although suffering from some disorder, shows a more typical, distorted arrangement of ligands; these results are discussed in terms of the tendency for soft, bulky ligands to promote symmetric, holodirected geometries. The ESI mass spectra of the adducts are reported, and yield [M−halide]⁺ ions.

text: Facile syntheses of four-membered aurathietane dioxide [Au–CHR-SO₂-CHR] ring systems, and the first isonitrile insertion reaction into a gold(III)–carbon bond The reactions of [Pt₂(μ-S)₂(PPh₃)₄] with excess PbBr₂ or PbI₂ in methanolic suspension result in the formation of the neutral lead(II) halide adducts [Pt₂(μ-S)₂(PPh₃)₄PbX₂] (X = Br, I). The X-ray structure determination of the lead iodide adduct reveals an essentially tetrahedral lead(II) centre, which is a rare coordination geometry for lead(II), which almost invariably is hemidirected, with a stereochemically active lone pair. In contrast, the structure of the PbBr₂ adduct, although suffering from some disorder, shows a more typical, distorted arrangement of ligands; these results are discussed in terms of the tendency for soft, bulky ligands to promote symmetric, holodirected geometries. The ESI mass spectra of the adducts are reported, and yield [M−halide]⁺ ions.

year: 2005-11-01

title: Synthesis and characterization of polymer-protected rhodium and palladium sols in mixed media

authors: Jaine, Jacob E.

subjects: Sol

abstract: A series of polymer-protectedrhodium and palladiumsols were generated in mixed (organic/aqueous) dispersion media. Protecting polymers used were PAA, PVP, PVA and an oligosaccharide-based protecting agent, arabinogalactan. This is the first systematic study of colloids generated in mixed solvent dispersion media with these protecting agents. The sols were characterized by TEM, UV/Vis spectrophotometry and Photon Correlation Spectroscopy (PCS). In general, the macroscopic stability of the sols depended on the protecting agent/organic cosolvent combination used, with a nonlinear dependence on cosolvent concentration. Observed sol stabilities correlated well with pre-existing hydrodynamic data for the protective polymers, e.g. radius of gyration data. Average particle size and polydispersity of all sols examined decreased as cosolvent concentration increased, with actual cosolvent concentration, protecting agent and reducing agent used influencing the extent of decrease. Sol particle sizes ranged from 0.8 nm to 6.0 nm with sol turbidities decreasing in parallel with the particle sizes. Hydrodynamic sizes (from PCS) tended to reflect the sols’ macroscopic stabilities. FTIR studies using adsorbed CO as a spectroscopic surface probe indicated decreases in the ν(CO)ads stretching frequency with an increase in cosolvent concentration due to competitive adsorption of CO with the cosolvent molecules on the metal colloid surfaces.

text: Synthesis and characterization of polymer-protected rhodium and palladium sols in mixed media A series of polymer-protectedrhodium and palladiumsols were generated in mixed (organic/aqueous) dispersion media. Protecting polymers used were PAA, PVP, PVA and an oligosaccharide-based protecting agent, arabinogalactan. This is the first systematic study of colloids generated in mixed solvent dispersion media with these protecting agents. The sols were characterized by TEM, UV/Vis spectrophotometry and Photon Correlation Spectroscopy (PCS). In general, the macroscopic stability of the sols depended on the protecting agent/organic cosolvent combination used, with a nonlinear dependence on cosolvent concentration. Observed sol stabilities correlated well with pre-existing hydrodynamic data for the protective polymers, e.g. radius of gyration data. Average particle size and polydispersity of all sols examined decreased as cosolvent concentration increased, with actual cosolvent concentration, protecting agent and reducing agent used influencing the extent of decrease. Sol particle sizes ranged from 0.8 nm to 6.0 nm with sol turbidities decreasing in parallel with the particle sizes. Hydrodynamic sizes (from PCS) tended to reflect the sols’ macroscopic stabilities. FTIR studies using adsorbed CO as a spectroscopic surface probe indicated decreases in the ν(CO)ads stretching frequency with an increase in cosolvent concentration due to competitive adsorption of CO with the cosolvent molecules on the metal colloid surfaces.

year: 2012

title: Tangi and State Funeral: Te Arikinui Dame Te Atairangikaahu and Prime Minister Norman Kirk

authors: McRae, Karyn Okeroa

subjects: Tangi

abstract: The tangi of Te Arikinui Dame Te Atairangikaahu (Te Arikinui) in 2006 paralleled the State funerals for New Zealand Prime Ministers like Norman Kirk who died in 1974. State funerals require the huge mobilization of people and resources and always attract the attention of the national and international media. The death of a Prime Minister is news worthy, but what of a minority indigenous fourth world leader like Te Arikinui? Why did her passing attract so much media attention? In this study I argue that media representation of the tangi of Te Arikinui was largely about social, cultural and symbolic capital. In media saturated societies such as Aotearoa/New Zealand, through mainstream media outlets like TV One News and the Waikato Times, Te Arikinui’s tangi event claimed a dominant space in the lives of Maori and non Maori alike. The data source includes print news media coverage of the tangi of Te Arikinui and the State funeral of Norman Kirk. Descriptive narrative and abductive analysis inform the methodology used in this study. As expected, print media reporting of both events progressed through the three stages identified by Durkheim, those of, separation, liminality and reincorporation. The ownership of death, the deceased and the continued possession of their mortal remains, itself a cultural object with symbolic and cultural capital, reflected the actual power and control of the possessor. State funerals and tangi are about the ritualized performance of grief and mourning, and require the appropriate social, cultural and symbolic capital for its enactment.

text: Tangi and State Funeral: Te Arikinui Dame Te Atairangikaahu and Prime Minister Norman Kirk The tangi of Te Arikinui Dame Te Atairangikaahu (Te Arikinui) in 2006 paralleled the State funerals for New Zealand Prime Ministers like Norman Kirk who died in 1974. State funerals require the huge mobilization of people and resources and always attract the attention of the national and international media. The death of a Prime Minister is news worthy, but what of a minority indigenous fourth world leader like Te Arikinui? Why did her passing attract so much media attention? In this study I argue that media representation of the tangi of Te Arikinui was largely about social, cultural and symbolic capital. In media saturated societies such as Aotearoa/New Zealand, through mainstream media outlets like TV One News and the Waikato Times, Te Arikinui’s tangi event claimed a dominant space in the lives of Maori and non Maori alike. The data source includes print news media coverage of the tangi of Te Arikinui and the State funeral of Norman Kirk. Descriptive narrative and abductive analysis inform the methodology used in this study. As expected, print media reporting of both events progressed through the three stages identified by Durkheim, those of, separation, liminality and reincorporation. The ownership of death, the deceased and the continued possession of their mortal remains, itself a cultural object with symbolic and cultural capital, reflected the actual power and control of the possessor. State funerals and tangi are about the ritualized performance of grief and mourning, and require the appropriate social, cultural and symbolic capital for its enactment.

year: 2010