title: Synthesis and structural characterisation of the lead–platinum sulfido aggregates [Pt₂(μ-S)₂(PPh₃)₄PbX₂] (X = Br, I); promotion of rare tetrahedral geometry for lead(II)

authors: Henderson, William

subjects: platinum complexes

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: Synthesis and structural characterisation of the lead–platinum sulfido aggregates [Pt₂(μ-S)₂(PPh₃)₄PbX₂] (X = Br, I); promotion of rare tetrahedral geometry for lead(II) 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: 2010-05-05

title: Defining a US defence diplomacy for Brazil at the beginning of the century

authors: Zirker, Daniel

subjects: diplomacy

abstract: At the beginning of the 1990s, the US military was apparently considered to be a significant threat by the Brazilian Armed Forces. Other military establishments in the Hemisphere likewise expressed a lack of confidence, and even a sense of fear, regarding the North Americans. After an ‘opening’ in military relations between Brazil and the United States, directed by General Barry McAfree, commander-in-chief of the US Southern Command (SOUTHCOM) in the mid 1990s, Brazilian military sentiment regarding the US marginally improved. Nevertheless, by the end of the 1990s and the beginning of this Century, the Brazilian Armed Forces again felt threatened by the unilateralism of the US military.
This work examines the the concept of ‘defense diplomacy’ and the process by which the Clinton Administration initiated an experiment in conjunction with the National Defense University (Fort Leslie McNair, Washington, DC), at the request of the Deputy Assitant Secretary of Defense for Western Hemisphere Affairs, that established between 1999 and 2001 a broader understanding of possible US defense diplomacy for the subsequent seven years. I was an invited participant in this experiment, along with more than two dozen North American and Latin American academics, including Brazilians, the aim of which was to complete a proposal under contract with the Defense Department. Although it was ended soon after the Bush Administration began, this experiment, and the broader concept of ‘defense diplomacy,’ may well have represented an important option for future hemispheric military relations.

text: Defining a US defence diplomacy for Brazil at the beginning of the century At the beginning of the 1990s, the US military was apparently considered to be a significant threat by the Brazilian Armed Forces. Other military establishments in the Hemisphere likewise expressed a lack of confidence, and even a sense of fear, regarding the North Americans. After an ‘opening’ in military relations between Brazil and the United States, directed by General Barry McAfree, commander-in-chief of the US Southern Command (SOUTHCOM) in the mid 1990s, Brazilian military sentiment regarding the US marginally improved. Nevertheless, by the end of the 1990s and the beginning of this Century, the Brazilian Armed Forces again felt threatened by the unilateralism of the US military.
This work examines the the concept of ‘defense diplomacy’ and the process by which the Clinton Administration initiated an experiment in conjunction with the National Defense University (Fort Leslie McNair, Washington, DC), at the request of the Deputy Assitant Secretary of Defense for Western Hemisphere Affairs, that established between 1999 and 2001 a broader understanding of possible US defense diplomacy for the subsequent seven years. I was an invited participant in this experiment, along with more than two dozen North American and Latin American academics, including Brazilians, the aim of which was to complete a proposal under contract with the Defense Department. Although it was ended soon after the Bush Administration began, this experiment, and the broader concept of ‘defense diplomacy,’ may well have represented an important option for future hemispheric military relations.

year: 2009

title: Whakaoranga taiao, whakaoranga tangata: The restorative, healing, and decolonising potential of environmental restoration

authors: Moore, Robert

abstract: This thesis explores the ways in which Māori who are involved in environmental restoration are able to use their experiences to reconnect with Te Ao Māori. Semi-structured interviews were conducted with three Māori who have been involved in environmental restoration in and around Kirikiriroa. These research participants were also able to speak to what they have observed in other restoration projects at their respective marae and comment broadly about this work as it is taking place across Aotearoa. It became clear through this research that the impacts of history and colonisation are still felt heavily by Māori in the environmental space today. For Māori involved in environmental restoration, this is a place where they are able to learn and share knowledge and reconnect with their Māoritanga. Environmental restoration can help restore wairua relationships with the whenua and strengthen Maori wellbeing through strengthening relationships with the whenua. Engaging in environmental restoration supports decolonisation as, for the aforementioned outcomes of doing so, being in these spaces supports the affirmation of an Indigenous identity.

text: Whakaoranga taiao, whakaoranga tangata: The restorative, healing, and decolonising potential of environmental restoration This thesis explores the ways in which Māori who are involved in environmental restoration are able to use their experiences to reconnect with Te Ao Māori. Semi-structured interviews were conducted with three Māori who have been involved in environmental restoration in and around Kirikiriroa. These research participants were also able to speak to what they have observed in other restoration projects at their respective marae and comment broadly about this work as it is taking place across Aotearoa. It became clear through this research that the impacts of history and colonisation are still felt heavily by Māori in the environmental space today. For Māori involved in environmental restoration, this is a place where they are able to learn and share knowledge and reconnect with their Māoritanga. Environmental restoration can help restore wairua relationships with the whenua and strengthen Maori wellbeing through strengthening relationships with the whenua. Engaging in environmental restoration supports decolonisation as, for the aforementioned outcomes of doing so, being in these spaces supports the affirmation of an Indigenous identity.

year: 2022