title: An electrospray mass spectrometry-directed survey of the coordination chemistry of the metalloligand [Pt₂(μ-S)₂(PPh₃)₄] with platinum(II) and palladium(II) chloride substrates: influence of metal–ligand lability on product type

authors: Fong, S.W. Audi

subjects: Sulfide complexes; Metalloligand; Platinum complexes; Palladium complexes

abstract: The reactivity of the metalloligand [Pt₂(μ-S)₂(PPh₃)₄] towards a wide range of platinum(II) and palladium(II) chloride complex substrates [L₂MCl₂] has been explored, using the technique of electrospray ionisation mass spectrometry to directly analyse reaction solutions. In the majority of cases, products are formed by addition of the ML₂²⁺ fragment to the {Pt₂S₂} core, giving trinuclear species [Pt₂(μ-S)₂(PPh₃)₄ML₂]²⁺. The adducts with Pt(diene) [diene=cyclo-octa-1,5-diene (cod), norbornadiene], Pd(cod), Pd(bipy) (bipy=2,2′-bipyridine), Pt(PMe₃)₂ and Pt(PTA)₂ (PTA=phosphatriaza-adamantane) moieties were synthesised and characterised on the macroscopic scale, with [Pt₂(μ-S)₂(PPh₃)₄Pt(cod)] (BF₄)₂ and [Pt₂(μ-S)₂(PPh₃)₄Pd(bipy)] (PF₆)₂ also characterised by X-ray diffraction studies. No metal scrambling was found to occur, as has been observed in some previous cases involving the related complexes [Pt₂(μ-Se)₂(PPh₃)₄] and [Pt₂(μ-S)₂(dppe)₂] (dppe=Ph₂PCH₂CH₂PPh₂). With cis-[PtCl₂(SOMe₂)₂] the species [Pt₂(μ-S)₂(PPh₃)₄PtCl(SOMe₂)]⁺ was formed, as a result of the lability of the SOMe2 ligand. With palladium(II)-phosphine systems, the observed product species is dependent on the phosphine; the bulky PPh₃ ligand in [PdCl₂(PPh₃)₂] leads primarily to the analogous known species [Pt₂(μ-S)₂(PPh₃)₄PdCl(PPh₃)]⁺, and a small amount of the metal-scrambled species [PtPd₂S₂(PPh₃)₅Cl]⁺. In contrast, [PdCl₂(PTA)₂], containing the small PTA ligand gave [Pt₂(μ-S)₂(PPh₃)₄Pd(PTA)₂]²⁺.
A survey of the reactions of [Pt₂(μ-S)₂(PPh₃)₄] with platinum(II) and palladium(II) dichloride substrates [L₂MCl₂] has been carried out using electrospray ionisation mass spectrometry; the dominant theme is the formation of dicationic species [Pt₂(μ-S)₂(PPh₃)₄ML₂]²⁺, but with some exceptions, which are discussed. The complexes [Pt₂(μ-S)₂(PPh₃)₄Pt(cod)](BF₄)₂ (cod=cyclo-octa-1,5-diene) and [Pt₂(μ-S)₂(PPh₃)₄Pd(bipy)] (PF₆)₂(bipy=2,2′-bipyridine) were characterised by X-ray diffraction studies.

text: An electrospray mass spectrometry-directed survey of the coordination chemistry of the metalloligand [Pt₂(μ-S)₂(PPh₃)₄] with platinum(II) and palladium(II) chloride substrates: influence of metal–ligand lability on product type The reactivity of the metalloligand [Pt₂(μ-S)₂(PPh₃)₄] towards a wide range of platinum(II) and palladium(II) chloride complex substrates [L₂MCl₂] has been explored, using the technique of electrospray ionisation mass spectrometry to directly analyse reaction solutions. In the majority of cases, products are formed by addition of the ML₂²⁺ fragment to the {Pt₂S₂} core, giving trinuclear species [Pt₂(μ-S)₂(PPh₃)₄ML₂]²⁺. The adducts with Pt(diene) [diene=cyclo-octa-1,5-diene (cod), norbornadiene], Pd(cod), Pd(bipy) (bipy=2,2′-bipyridine), Pt(PMe₃)₂ and Pt(PTA)₂ (PTA=phosphatriaza-adamantane) moieties were synthesised and characterised on the macroscopic scale, with [Pt₂(μ-S)₂(PPh₃)₄Pt(cod)] (BF₄)₂ and [Pt₂(μ-S)₂(PPh₃)₄Pd(bipy)] (PF₆)₂ also characterised by X-ray diffraction studies. No metal scrambling was found to occur, as has been observed in some previous cases involving the related complexes [Pt₂(μ-Se)₂(PPh₃)₄] and [Pt₂(μ-S)₂(dppe)₂] (dppe=Ph₂PCH₂CH₂PPh₂). With cis-[PtCl₂(SOMe₂)₂] the species [Pt₂(μ-S)₂(PPh₃)₄PtCl(SOMe₂)]⁺ was formed, as a result of the lability of the SOMe2 ligand. With palladium(II)-phosphine systems, the observed product species is dependent on the phosphine; the bulky PPh₃ ligand in [PdCl₂(PPh₃)₂] leads primarily to the analogous known species [Pt₂(μ-S)₂(PPh₃)₄PdCl(PPh₃)]⁺, and a small amount of the metal-scrambled species [PtPd₂S₂(PPh₃)₅Cl]⁺. In contrast, [PdCl₂(PTA)₂], containing the small PTA ligand gave [Pt₂(μ-S)₂(PPh₃)₄Pd(PTA)₂]²⁺.
A survey of the reactions of [Pt₂(μ-S)₂(PPh₃)₄] with platinum(II) and palladium(II) dichloride substrates [L₂MCl₂] has been carried out using electrospray ionisation mass spectrometry; the dominant theme is the formation of dicationic species [Pt₂(μ-S)₂(PPh₃)₄ML₂]²⁺, but with some exceptions, which are discussed. The complexes [Pt₂(μ-S)₂(PPh₃)₄Pt(cod)](BF₄)₂ (cod=cyclo-octa-1,5-diene) and [Pt₂(μ-S)₂(PPh₃)₄Pd(bipy)] (PF₆)₂(bipy=2,2′-bipyridine) were characterised by X-ray diffraction studies.

year: 2004-05-01

title: Boundaries of absolute protection: distribution of benefit and harm to birds through law and planning in New Zealand

authors: Wallace, Philippa Jane

subjects: Law

abstract: Endemic birds in New Zealand are under threat, and increasingly so, as human activity reshapes the land, reconstitutes the water, consumes space and resources and alters faunal composition. The decline of biodiversity is a pressing concern globally and the unique nature of the endemic fauna of New Zealand provides impetus for concern. 
Examination of the state of birds and analysis of the response of New Zealand law to the agents of decline is the key contribution of this research. The substance and operation of New Zealand law is examined to determine its influence upon the distribution of benefit and burden to New Zealand birds. Six case study birds: the black petrel, dotterel, kokako, godwit, sooty shearwater, and the wrybill are studied to elucidate these matters.
In examining distribution of harm and benefit, a particular focus of the research is upon the degree of care that is applied to protecting birds through the law and related planning instruments. By assessing the principles, criteria and methods applied to protecting birds, the research identifies that an objective of avoidance of harm to indigenous Threatened or At Risk species, their habitats, and ecosystems upon which they depend, will benefit birds. It concludes that conservation status, as opposed to habitat or sectoral dispensation, is an important determinant for application of the standard, as this provides the most consistently protective approach. In addition, it is demonstrated that where uncertainty or ignorance arises as to existence or level of harm, the use of precaution and giving the benefit of the doubt to nature is important for enhancing protection.
New Zealand conservation law is analysed at the international level in conjunction with species and habitat protection at the domestic level. International agreements, the Wildlife Act 1953, the Conservation Act 1987, the Resource Management Act 1991 and related policy and plans are examined. Although at times strongly beneficial, the research concludes that the arrangements made by the law are wanting. An important contribution of the research is to demonstrate the deficiencies, which can be separated into three classes: the problem of standard, the problem of consistency and integration, and the problem of implementation.
These problems constrain the protective force of the law. Fragmentation and lack of a strong and consistent protective standard limit protection of birds against competing social, economic and cultural factors. The law requires revision. Species protection calls for particular attention. The Wildlife Act 1953 maintains a standard of absolute protection of birds, but the research demonstrates the many ways in which this standard is compromised. Greater strategic planning and integration is required, particularly with regard to human development. Interrelationships between the statutes, including that between the Wildlife Act 1953 and the RMA 1991, require addressing. Inadequate implementation of existing law compounds these matters, and the research identifies a range of aspects where gains for species could be made. It concludes with a series of recommendations directed at the identified problems.

Pip Wallace 2014 PhD thesis
pwallace@waikato.ac.nz

text: Boundaries of absolute protection: distribution of benefit and harm to birds through law and planning in New Zealand Endemic birds in New Zealand are under threat, and increasingly so, as human activity reshapes the land, reconstitutes the water, consumes space and resources and alters faunal composition. The decline of biodiversity is a pressing concern globally and the unique nature of the endemic fauna of New Zealand provides impetus for concern. 
Examination of the state of birds and analysis of the response of New Zealand law to the agents of decline is the key contribution of this research. The substance and operation of New Zealand law is examined to determine its influence upon the distribution of benefit and burden to New Zealand birds. Six case study birds: the black petrel, dotterel, kokako, godwit, sooty shearwater, and the wrybill are studied to elucidate these matters.
In examining distribution of harm and benefit, a particular focus of the research is upon the degree of care that is applied to protecting birds through the law and related planning instruments. By assessing the principles, criteria and methods applied to protecting birds, the research identifies that an objective of avoidance of harm to indigenous Threatened or At Risk species, their habitats, and ecosystems upon which they depend, will benefit birds. It concludes that conservation status, as opposed to habitat or sectoral dispensation, is an important determinant for application of the standard, as this provides the most consistently protective approach. In addition, it is demonstrated that where uncertainty or ignorance arises as to existence or level of harm, the use of precaution and giving the benefit of the doubt to nature is important for enhancing protection.
New Zealand conservation law is analysed at the international level in conjunction with species and habitat protection at the domestic level. International agreements, the Wildlife Act 1953, the Conservation Act 1987, the Resource Management Act 1991 and related policy and plans are examined. Although at times strongly beneficial, the research concludes that the arrangements made by the law are wanting. An important contribution of the research is to demonstrate the deficiencies, which can be separated into three classes: the problem of standard, the problem of consistency and integration, and the problem of implementation.
These problems constrain the protective force of the law. Fragmentation and lack of a strong and consistent protective standard limit protection of birds against competing social, economic and cultural factors. The law requires revision. Species protection calls for particular attention. The Wildlife Act 1953 maintains a standard of absolute protection of birds, but the research demonstrates the many ways in which this standard is compromised. Greater strategic planning and integration is required, particularly with regard to human development. Interrelationships between the statutes, including that between the Wildlife Act 1953 and the RMA 1991, require addressing. Inadequate implementation of existing law compounds these matters, and the research identifies a range of aspects where gains for species could be made. It concludes with a series of recommendations directed at the identified problems.

Pip Wallace 2014 PhD thesis
pwallace@waikato.ac.nz

year: 2014

title: Who owns native nature? Discourses of rights to land, culture, and knowledge in New Zealand

authors: Goldsmith, Michael

subjects: indigenous cultures

abstract: Michael Brown famously asked ‘Who owns native culture?’ This paper revisits that question by analyzing what happens to culture when the culturally defined boundary between it and nature becomes salient in the context of disputes between indigenous and settler populations. My case study is the dispute between the New Zealand government and Maori tribal groupings concerning ownership of the foreshore and seabed. Having been granted the right to test their claims in court in 2003, Maori groups were enraged when the government legislated the right out of existence in 2004. Though the reasons for doing so were clearly political, contrasting cultural assumptions appeared to set Maori and Pakeha (New Zealanders of European origin) at odds. While couching ownership of part of nature as an IPR issue may seem counter-intuitive, I argue that as soon as a property claim destabilizes the nature/culture boundary, IPR discourse becomes pertinent.

text: Who owns native nature? Discourses of rights to land, culture, and knowledge in New Zealand Michael Brown famously asked ‘Who owns native culture?’ This paper revisits that question by analyzing what happens to culture when the culturally defined boundary between it and nature becomes salient in the context of disputes between indigenous and settler populations. My case study is the dispute between the New Zealand government and Maori tribal groupings concerning ownership of the foreshore and seabed. Having been granted the right to test their claims in court in 2003, Maori groups were enraged when the government legislated the right out of existence in 2004. Though the reasons for doing so were clearly political, contrasting cultural assumptions appeared to set Maori and Pakeha (New Zealanders of European origin) at odds. While couching ownership of part of nature as an IPR issue may seem counter-intuitive, I argue that as soon as a property claim destabilizes the nature/culture boundary, IPR discourse becomes pertinent.

year: 2009