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: Surrogate motherhood: The professional model

authors: van Zyl, Liezl

abstract: This paper discusses surrogate motherhood.

text: Surrogate motherhood: The professional model This paper discusses surrogate motherhood.

year: 2017

title: Desirable attributes for medical graduates: The health aspirations and needs of Maaori living in Te Rohe Pootae

authors: Maikuku, Victoria Louisa Wikitoria

abstract: Health disparities for Maaori, the tangata whenua of Aotearoa New Zealand, are prevalent when compared to the health of European New Zealanders, and even more so in remote and rural communities where access to health-care services is limited. Moreover, Maaori are underrepresented in the medical workforce in which there is a serious and escalating shortage of doctors and nurses.

In the context of the University of Waikato’s proposal to establish a Graduate Entry Medical School, Te Huataki Waiora School of Health has identified the need for a collaborative approach to ‘growing’ a fit-for-purpose health workforce with the skills and commitment to care for and work with Maaori (and Pacific peoples) living in remote and rural communities. This study thus explores the health perspectives, needs, and aspirations of Maaori living in and around the King Country rural service towns of Te Kuiti and OOtorohanga. Conducted by a Ngaati Maniapoto tribal member, the location for the study is known by Maaori as Te Rohe Pootae - the lands of Rereahu/Maniapoto, to which the Waikato people sort refuge after the invasion and confiscation of their lands in the 1860s. The perspectives, needs, and aspirations of Pacific peoples living in these communities have been explored in a ‘sister’ Masters study conducted by Janina Galewski.

The present exploratory study incorporates a co-design research process underpinned by an Indigenous health framework with Kaupapa Maaori values. Kanohi ki te kanohi (face to face) semi-structured interviews were conducted with 30 community members, 11 males and 19 females aged 18 years and over. The data analysis included a combination of values, verses and holistic, and provisional coding methods (focused, thematic, descriptive) (Saldana, 2021).

The findings reveal that these community members view themselves as either rural or remote based on distance, access to services, and geographic isolation, but not population numbers. In terms of services, they want a mobile health workforce including clinics, carers, doctors, nurses; mental health workers who are equipped with the resources and time needed to reach and serve their patients; and better access to dialysis and related services. The research also identifies three healthcare strategies. When ill or injured, one-third of the group go directly to their GP; one-third try other things before seeking medical assistance, including going home to their parents and/or to their marae for comfort and advice, ‘going bush’ to (re)connect with nature, and forms of pure (cleansing rituals); and although the remaining third are registered with medical centres they do everything they can to avoid seeing a doctor at all. Instead, they rely on rongoaa and other ‘complementary and alternative’ treatments such as physiotherapists, chiropractors, osteopaths, and other healers. 

Adopting and adapting a table created by Woolley et al. (2013), the findings also revealed three sets of desirable attributes for medical graduates (and other healthcare professionals): Skill-based attributes include quality care and communication skills, knowledge-based attributes include medical knowledge and culturally appropriate knowledge, while attitude-based attributes include personality and community engagement. This framework can be used to inform a medical education curriculum, with a specific emphasis on the health needs and aspirations of Maaori living in rural and remote communities.

text: Desirable attributes for medical graduates: The health aspirations and needs of Maaori living in Te Rohe Pootae Health disparities for Maaori, the tangata whenua of Aotearoa New Zealand, are prevalent when compared to the health of European New Zealanders, and even more so in remote and rural communities where access to health-care services is limited. Moreover, Maaori are underrepresented in the medical workforce in which there is a serious and escalating shortage of doctors and nurses.

In the context of the University of Waikato’s proposal to establish a Graduate Entry Medical School, Te Huataki Waiora School of Health has identified the need for a collaborative approach to ‘growing’ a fit-for-purpose health workforce with the skills and commitment to care for and work with Maaori (and Pacific peoples) living in remote and rural communities. This study thus explores the health perspectives, needs, and aspirations of Maaori living in and around the King Country rural service towns of Te Kuiti and OOtorohanga. Conducted by a Ngaati Maniapoto tribal member, the location for the study is known by Maaori as Te Rohe Pootae - the lands of Rereahu/Maniapoto, to which the Waikato people sort refuge after the invasion and confiscation of their lands in the 1860s. The perspectives, needs, and aspirations of Pacific peoples living in these communities have been explored in a ‘sister’ Masters study conducted by Janina Galewski.

The present exploratory study incorporates a co-design research process underpinned by an Indigenous health framework with Kaupapa Maaori values. Kanohi ki te kanohi (face to face) semi-structured interviews were conducted with 30 community members, 11 males and 19 females aged 18 years and over. The data analysis included a combination of values, verses and holistic, and provisional coding methods (focused, thematic, descriptive) (Saldana, 2021).

The findings reveal that these community members view themselves as either rural or remote based on distance, access to services, and geographic isolation, but not population numbers. In terms of services, they want a mobile health workforce including clinics, carers, doctors, nurses; mental health workers who are equipped with the resources and time needed to reach and serve their patients; and better access to dialysis and related services. The research also identifies three healthcare strategies. When ill or injured, one-third of the group go directly to their GP; one-third try other things before seeking medical assistance, including going home to their parents and/or to their marae for comfort and advice, ‘going bush’ to (re)connect with nature, and forms of pure (cleansing rituals); and although the remaining third are registered with medical centres they do everything they can to avoid seeing a doctor at all. Instead, they rely on rongoaa and other ‘complementary and alternative’ treatments such as physiotherapists, chiropractors, osteopaths, and other healers. 

Adopting and adapting a table created by Woolley et al. (2013), the findings also revealed three sets of desirable attributes for medical graduates (and other healthcare professionals): Skill-based attributes include quality care and communication skills, knowledge-based attributes include medical knowledge and culturally appropriate knowledge, while attitude-based attributes include personality and community engagement. This framework can be used to inform a medical education curriculum, with a specific emphasis on the health needs and aspirations of Maaori living in rural and remote communities.

year: 2022