title: Electrospray-friendly ligands for the mass spectral analysis of transition-metal complexes

authors: Decker, Corry

abstract: The key aim of this project was to develop the concept of electrospray-friendly ligands as a new ionisation method for the analysis of neutral metal complexes by electrospray mass spectrometry (ESMS). This involved introducing active functional groups into traditional ligands which do not otherwise undergo chemical ionisation under ESMS conditions.

Electrospray-friendly ligands (as illustrated above for PPh₃ derivatives) were incorporated into a series of metal carbonyl complexes of Mo, Fe and Ru, metal halide complexes of Pd, Pt and Au, and a number of zero-valent complexes of Pt and Pd. All carbonyl complexes with ES-friendly phosphine, arsine and stibine ligands ionised by protonation, yielding strong [M + H]⁺ ions as the only signals in the spectrum. The metal halide complexes followed the known halide-loss mechanism. Pt(0) and Pd(0) complexes did not require functionalised ligands, as their PPh₃ derivatives already gave [M +H]⁺ ions. Mo and W carbonyl complexes of the two ‘naturally’ electrospray friendly ligands tpa (tpa = 1,3,5-triaza-7-phosphaadamantane) and tcep [tcep = tris(2-cyanoethyl)phosphine] could also be studied readily by ESMS. While all tpa complexes gave [M + H]⁺ ions, complexes of tcep preferred ionisation by NH₄⁺. The ionisation efficiencies of selected ligands and complexes are discussed.

Thiolate complexes of Ni, Pd, Pt, Au and Hg were prepared using the ligands SC₆H₄OMe-p (S*) and p-SC₅H₄N (S•), but only the S•-complexes reliably underwent the protonation-type mechanism. The Cd-thiolate complexes [Cd₄(SPh)₁₀]²⁻, [S₄Cd₁₀(SPh)₁₆]⁴⁻ and [S₄Cd₁₀(SPh)₂₈]²⁻ underwent rapid ligand exchange with S*, but yielded insoluble products with S•. The complexes [Pt₂(μ-S)₂(L)₂] (L = PPh₃, P*, P**, P***. P•. As***¹) were prepared, and by means of ESMS, aspects of ligand exchange as well as reactivity towards other metal centres were investigated.

Isonitrile derivatives of [Fe₃(CO)₁₂] and [Ru₃CO)₁₂] were prepared by ligand exchange with CNPh, CNC₆H₄OMe-p (CNPh*) and tosylmethylisocyanide. Substitution was observed for up to six CO ligands. Pyrolysis of [Fe₃(CO)₁₁(L)] and [Fe₃(CO)₁₀(L)₂] (L =CNPh, CNPh*) led to the products [Fe₃(CO)₉(μ₃ - η²-L)] and [Fe₃(CO)₈(μ₃-η²-L) (L)], respectively. All complexes could be studied by ESMS as their [M + H]⁺, [M + MeO]⁻ or  [M – H]⁻ ions, depending on the exact nature of the analyte. [Fe₃(CO)₁₀(CNPh)₂] was characterised structurally (below) and revealed an unprecedented substitution pattern, together with unexpected partial disorder in the metal framework.

Detection by ESMS of products of the type [Ru₄(CO) ₁₄₋ₙ(L)ₙ] (L = CNPh, CNPh*; n =2-4) in the reactions with ruthenium carbonyl led to the isolation and structural characterisation of [Ru₄(CO)₁₂(CNPh)₄], which is the only fully characterised isonitrile derivative of [Ru₃(CO)₁₂] with four metal atoms and exhibits an unusual imine-type bonding mode for the bridging isonitrile ligands.
________________________
¹As*** = As(C₆H₄OMe-p)₃

text: Electrospray-friendly ligands for the mass spectral analysis of transition-metal complexes The key aim of this project was to develop the concept of electrospray-friendly ligands as a new ionisation method for the analysis of neutral metal complexes by electrospray mass spectrometry (ESMS). This involved introducing active functional groups into traditional ligands which do not otherwise undergo chemical ionisation under ESMS conditions.

Electrospray-friendly ligands (as illustrated above for PPh₃ derivatives) were incorporated into a series of metal carbonyl complexes of Mo, Fe and Ru, metal halide complexes of Pd, Pt and Au, and a number of zero-valent complexes of Pt and Pd. All carbonyl complexes with ES-friendly phosphine, arsine and stibine ligands ionised by protonation, yielding strong [M + H]⁺ ions as the only signals in the spectrum. The metal halide complexes followed the known halide-loss mechanism. Pt(0) and Pd(0) complexes did not require functionalised ligands, as their PPh₃ derivatives already gave [M +H]⁺ ions. Mo and W carbonyl complexes of the two ‘naturally’ electrospray friendly ligands tpa (tpa = 1,3,5-triaza-7-phosphaadamantane) and tcep [tcep = tris(2-cyanoethyl)phosphine] could also be studied readily by ESMS. While all tpa complexes gave [M + H]⁺ ions, complexes of tcep preferred ionisation by NH₄⁺. The ionisation efficiencies of selected ligands and complexes are discussed.

Thiolate complexes of Ni, Pd, Pt, Au and Hg were prepared using the ligands SC₆H₄OMe-p (S*) and p-SC₅H₄N (S•), but only the S•-complexes reliably underwent the protonation-type mechanism. The Cd-thiolate complexes [Cd₄(SPh)₁₀]²⁻, [S₄Cd₁₀(SPh)₁₆]⁴⁻ and [S₄Cd₁₀(SPh)₂₈]²⁻ underwent rapid ligand exchange with S*, but yielded insoluble products with S•. The complexes [Pt₂(μ-S)₂(L)₂] (L = PPh₃, P*, P**, P***. P•. As***¹) were prepared, and by means of ESMS, aspects of ligand exchange as well as reactivity towards other metal centres were investigated.

Isonitrile derivatives of [Fe₃(CO)₁₂] and [Ru₃CO)₁₂] were prepared by ligand exchange with CNPh, CNC₆H₄OMe-p (CNPh*) and tosylmethylisocyanide. Substitution was observed for up to six CO ligands. Pyrolysis of [Fe₃(CO)₁₁(L)] and [Fe₃(CO)₁₀(L)₂] (L =CNPh, CNPh*) led to the products [Fe₃(CO)₉(μ₃ - η²-L)] and [Fe₃(CO)₈(μ₃-η²-L) (L)], respectively. All complexes could be studied by ESMS as their [M + H]⁺, [M + MeO]⁻ or  [M – H]⁻ ions, depending on the exact nature of the analyte. [Fe₃(CO)₁₀(CNPh)₂] was characterised structurally (below) and revealed an unprecedented substitution pattern, together with unexpected partial disorder in the metal framework.

Detection by ESMS of products of the type [Ru₄(CO) ₁₄₋ₙ(L)ₙ] (L = CNPh, CNPh*; n =2-4) in the reactions with ruthenium carbonyl led to the isolation and structural characterisation of [Ru₄(CO)₁₂(CNPh)₄], which is the only fully characterised isonitrile derivative of [Ru₃(CO)₁₂] with four metal atoms and exhibits an unusual imine-type bonding mode for the bridging isonitrile ligands.
________________________
¹As*** = As(C₆H₄OMe-p)₃

year: 2002

title: A Service for Audio Icon and Audio Books in the Mobile Tourist Information System (TIP) via the Greenstone Digital Library

authors: Gao, Xin

subjects: Audio Icon

abstract: This project provides an audio notification about nearby tourism place to visit (named sight in this thesis), a chapter based Audio Books related to the current sight and involving Digital Library to provide text for the Audio Books for the Tourist Information Provider on a mobile device (TIP). The current system plays a background sound for the sight only when the system displays the specific information for that sight after user selects it. This has been improved to provide a notification by which to receive audios from the recommendation service, and then keep sending audio data to clients on real time. So users can know the sight nearby before they look at their screen. The limitation of current Audio Books is that it only provides Audio Books when the books start from the current sight. This problem is solved by providing a list of books that has any chapter related to that sight, and users can add them into a now-playing list. The Travel Planning Service has been involved to place the Audio Books chapters into the now-playing list based on the order of the visiting sight in their plan. The TIP/Greenstone Service, which can load particular text from Greenstone Digital Library into TIP, has been involved in this project to provide related chapter-based text for those Audio Books. The implemented prototype has been evaluated on effeteness and performance based on the purpose of this project. The result has been discussed to prove it has effectively solved the problem described above. Finally, the result of the experiment on distinguishing audio, and technology for implementation and audio transfers, has been left for future study.

text: A Service for Audio Icon and Audio Books in the Mobile Tourist Information System (TIP) via the Greenstone Digital Library This project provides an audio notification about nearby tourism place to visit (named sight in this thesis), a chapter based Audio Books related to the current sight and involving Digital Library to provide text for the Audio Books for the Tourist Information Provider on a mobile device (TIP). The current system plays a background sound for the sight only when the system displays the specific information for that sight after user selects it. This has been improved to provide a notification by which to receive audios from the recommendation service, and then keep sending audio data to clients on real time. So users can know the sight nearby before they look at their screen. The limitation of current Audio Books is that it only provides Audio Books when the books start from the current sight. This problem is solved by providing a list of books that has any chapter related to that sight, and users can add them into a now-playing list. The Travel Planning Service has been involved to place the Audio Books chapters into the now-playing list based on the order of the visiting sight in their plan. The TIP/Greenstone Service, which can load particular text from Greenstone Digital Library into TIP, has been involved in this project to provide related chapter-based text for those Audio Books. The implemented prototype has been evaluated on effeteness and performance based on the purpose of this project. The result has been discussed to prove it has effectively solved the problem described above. Finally, the result of the experiment on distinguishing audio, and technology for implementation and audio transfers, has been left for future study.

year: 2007

title: Restoring the flow: Challenging the existing management frameworks to integrate Mātauranga Māori

authors: Hall, Tredegar Rangiātea

subjects: tangata whenua water management

abstract: Within the context of the current regimes of fresh water management in Aotearoa, this thesis is an exploration of the significance of freshwater to Māori; our rangatiratanga, Treaty rights and ownership. The Māori world view and the way this relates to fresh water is described and contrasted with the principles and practices of water management in the contemporary neo-liberal governance structures of this country. The impacts of the commodification of water through ownership rights, the limited monitoring capacity and the inability to provide a governance structure that will work across diverse environments are seen to threaten the sustainability of a critical part of our environment. The primary focus of on this research is on the relationship between the exclusion of tangata whenua from decision making in resource management and the degradation of the environment.
 
The thesis comments on the development of resource management legislation and actions of the state in Aotearoa, and uses post-colonial theory as a starting point to document the subordinate relationship of Māori within contemporary governance. This has privileged mono-cultural and neoliberal forms of water management that has scarred Papatūānuku and threatens human sustainability into the future.
    
The recent co-management agreement for the Waikato River is the specific case study against which a recent effort to reduce the alienation of Māori is viewed. A kaupapa Māori methodology is used to acquire and understand the importance of mātauranga Māori/ Traditional Ecological Knowledge (TEK) and what is required for these principles to enhance water management practices within the case study area. The original contribution of the work is drawn from interviews conducted with Māori and others who are involved in or informed by the commitment to explore co-management sustainable management options. These views are woven into a substantial and interpretative commentary on the role of Māori in future water governance.

The thesis argues that the best way to enhance water management and environmental protection is by inducing a planning paradigm shift where tangata whenua are given greater influence in environmental decision making that resembles an equal Treaty of Waitangi partnership, where the ethic of kaitiakitanga is empowered. Such a strategy would allow decision making regarding water and environmental management to be more focused on what is best for the resource and its survival rather than what most cost effective for some owners of water rights. Encouraging the acceptance of mātauranga Māori and incorporating more efficient and sustainable innovative technologies can restore the mauri of water in our place.

text: Restoring the flow: Challenging the existing management frameworks to integrate Mātauranga Māori Within the context of the current regimes of fresh water management in Aotearoa, this thesis is an exploration of the significance of freshwater to Māori; our rangatiratanga, Treaty rights and ownership. The Māori world view and the way this relates to fresh water is described and contrasted with the principles and practices of water management in the contemporary neo-liberal governance structures of this country. The impacts of the commodification of water through ownership rights, the limited monitoring capacity and the inability to provide a governance structure that will work across diverse environments are seen to threaten the sustainability of a critical part of our environment. The primary focus of on this research is on the relationship between the exclusion of tangata whenua from decision making in resource management and the degradation of the environment.
 
The thesis comments on the development of resource management legislation and actions of the state in Aotearoa, and uses post-colonial theory as a starting point to document the subordinate relationship of Māori within contemporary governance. This has privileged mono-cultural and neoliberal forms of water management that has scarred Papatūānuku and threatens human sustainability into the future.
    
The recent co-management agreement for the Waikato River is the specific case study against which a recent effort to reduce the alienation of Māori is viewed. A kaupapa Māori methodology is used to acquire and understand the importance of mātauranga Māori/ Traditional Ecological Knowledge (TEK) and what is required for these principles to enhance water management practices within the case study area. The original contribution of the work is drawn from interviews conducted with Māori and others who are involved in or informed by the commitment to explore co-management sustainable management options. These views are woven into a substantial and interpretative commentary on the role of Māori in future water governance.

The thesis argues that the best way to enhance water management and environmental protection is by inducing a planning paradigm shift where tangata whenua are given greater influence in environmental decision making that resembles an equal Treaty of Waitangi partnership, where the ethic of kaitiakitanga is empowered. Such a strategy would allow decision making regarding water and environmental management to be more focused on what is best for the resource and its survival rather than what most cost effective for some owners of water rights. Encouraging the acceptance of mātauranga Māori and incorporating more efficient and sustainable innovative technologies can restore the mauri of water in our place.

year: 2012