Copper and silver complexes bearing flexible hybrid scorpionate ligand mpBm.

The addition of flexible scorpionate ligand, [mpBm]⁻{i.e. HB(mt)2(mp), where mt = methyl-2-mercaptoimidazole and mp = 2-mercaptopyridine} to group eleven centres is reported for the first time. The coordination of this hybrid ligand to copper(I) and silver(I) centres in the presence of triphenylphosphine and trialkylphosphine co-ligands has been investigated. The trialkylphosphines coordinates to both copper and silver centres while the less basic triarylphosphine only successfully coordinates to the copper centre. Structural characterisation of [Cu{HB(mt)2(mp)}(PPh3)], [Cu{HB(mt)2(mp)}(PCy3)] and [Ag{HB(mt)2(mp)}(PCy3)] confirm κ³-SSH coordination modes for ligand where one of the mt 'arms' and the mp 'arm' of the scorpionate ligand are coordinated to the metal centre. The second mt 'arm' remains uncoordinated in all three complexes. A comparison has been made with the parent sulfur based scorpionate ligand, [Tm]⁻{HB(mt)3}.

An exploratory study of oncology specialists' understanding of the preferences of young people living with cancer.

Awareness about the specific needs of Adolescents and Young Adults (AYA) aged 15-25 with a diagnosis of cancer has grown rapidly over the past 10 years. To improve outcomes for these patients it is essential that services are developed within youth friendly models. This requires awareness by healthcare professionals of unique biological, genetic, epidemiological, psychological, social, and cultural factors that affect the AYA population. This study sought to explore oncology professionals understanding of the healthcare preferences of AYAs with cancer receiving treatment at a specialist cancer centre. Participants comprised 60 professionals in allied health (n = 15); nursing (n = 32); oncology (n = 6) and those from the Victorian AYA Cancer Service (n = 7). A questionnaire, developed from pilot work, collected demographic information, investigated professionals' top five perceived issues for AYAs, and examined perceptions in the areas of communication; information provision; environment; services; education, employment and social life, fertility and sexuality; support and survivorship. Results illustrate that, with a strong focus on survival and physical wellbeing, professionals significantly underestimate the breadth of AYA psychosocial concerns. The findings further indicate: that young people report different healthcare preferences compared to those reported by professionals; there are varying levels of professional skill, experience and confidence; there are significant workforce development and support needs for professionals; and AYA models of care require rigorous evaluation to ensure the improvement of outcomes for young people living with cancer.

The relationship between unmet needs and distress amongst young people with cancer.

PURPOSE: Most psychosocial research in cancer has been restricted to paediatric or older adult populations. This study aimed to explore psychological distress and unmet needs in adolescents and young adults (AYA) with cancer and identify predictors of distress among demographic and illness characteristics and supportive care needs. METHODS: Fifty-three patients between 16 and 30 years completed a cross-sectional survey, administered shortly after presentation to an AYA oncology service and within 4 months of diagnosis. Measures included the Beck Depression Inventory-Fast Screen (BDI-FS), State-Trait Anxiety Inventory-State Form (STAI-S) and the Supportive Care Needs Survey. Level of distress-related sypmtomatology in this population was based on previous work, whereby a cut-off score of 4 or greater was used for the BDI-FS, and one standard deviation above the sample population mean was used for the STAI-S. RESULTS: Prevalence of distress (25%) was lower than that found previously in AYA with cancer. Physical and daily living needs were the most frequently unmet needs overall, followed by psychological needs, health system and information needs and care and support needs. Lastly, being pre-treatment predicted increased depression and state anxiety, while having treatment post-surgery predicted reduced state anxiety. After controlling for treatment status, however, the main predictors of depression and state anxiety were physical and daily living needs and health system and information needs, respectively. CONCLUSIONS: Lower levels of distress and unmet psychological needs were related to the few participants (17%) in this study who were pre-treatment, when distress was most likely. However, physical needs and information needs, which are almost inevitable throughout treatment and beyond, were more important predictors of distress. Further exploration must consider the psychosocial difficulties underlying this association and the needs of AYA at transitions between critical periods in their cancer journey (i.e., upon diagnosis, during treatment, etc.).

Adolescents & young adults: issues in transition from active therapy into follow-up care.

PURPOSE: The development of services focused on addressing the needs of Adolescent & Young Adult (AYA) cancer patients as they transition from active therapy into follow-up care is an area of growth, development and research across the globe. This is important as much of the empirical literature and service development to date has focused on children or older adults. In Victoria, Australia, as elsewhere, survivorship studies focusing on the AYA age group are needed to answer questions regarding their medical, psychological and social needs. This article examines the qualitative exploration of the findings of a small focus group study with young people and the subsequent development of a practice framework by the onTrac@PeterMac Victorian Adolescent & Young Adult Cancer Service. METHOD: Eight young people, with a mean age at diagnosis of 24 years and 8 months, participated in a 3h focus group. A qualitative analytic approach was utilized to examine themes. KEY RESULTS: The participants identified a number of survivorship concerns relating to three broad categories: finishing treatment, ongoing health concerns and future directions. CONCLUSIONS: The research findings supported the development of a practice framework designed to assist in the management of AYA living with cancer in Victoria. Results also supported previously documented evidence that indicate gaps in cancer knowledge and services provided to this age group. Further collaborative research is required to understand AYA treatment and survivorship issues to assist in the development of more formalised aged appropriate protocols.

A new family of flexible scorpionate ligands based on 2-mercaptopyridine.

A new family of flexible scorpionate ligands based on 2-mercaptopyridine is reported. The tris- and bis-substituted ligands, K[HB(mp)(3)] (1) and Na[H(2)B(mp)(2)] (2) (mp = 2-mercaptopyridine) have been prepared and fully characterised. The structural characterisation of 1 reveals an unprecedented mu(3)-kappa(3)-SS'H-eta(1)eta(1)eta(2)-kappa(2)-S''C-eta(1)eta(1)-kappa(1)-S'-eta(1) coordination mode. The coordination of both 1 and 2 to copper(I) complexes containing triphenylphosphine and tricyclohexylphosphine co-ligands is investigated suggesting kappa(3)-SSS coordination modes for [Cu{HB(mp)(3)}(PR(3))] {where R = Ph (3); R = Cy, (4)} and kappa(3)-SSH coordination modes for [Cu{H(2)B(mp)(2)}(PR(3))] {where R = Ph (5); R = Cy (6)} the latter confirmed by structural characterisation of 5. A structural comparison with the sulfur based scorpionates, HB(mt)(3) and H(2)B(mt)(2) (mt = methyl-2-mercaptoimidazole) is made in terms of the degree of tautomerisation of the heterocyclic rings.

Synthesis of rhodium(I) and iridium(I) complexes of chiral N-heterocyclic carbenes and their application to asymmetric transfer hydrogenation.

Rhodium and iridium complexes of chiral NHC-phenolimine and NHC-amine ligands have been prepared and studied for asymmetric transfer hydrogenation. X-ray and NMR spectroscopy show that for NHC-phenolimine complexes abstraction of chloride results in a change in ligand coordination from NHC only to chelating NHC-imine. Complexes of NHC-amines are inactive for transfer hydrogenation, whereas complexes of NHC-phenolimines are active at room temperature for a range of aryl containing ketones. Enantioselectivity is very sensitive to the NHC N-substituent resulting in a switch in the predominant enantiomer.

Structural variation, dynamics, and catalytic application of palladium(II) complexes of di-N-heterocyclic carbene-amine ligands.

A series of palladium(II) complexes incorporating di-NHC-amine ligands has been prepared and their structural, dynamic and catalytic behaviour investigated. The complexes [trans-(kappa(2)-(tBu)CN(Bn)C(tBu))PdCl(2)] (12) and [trans-(kappa(2)-(Mes)CN(H)C(Mes))PdCl(2)] (13) do not exhibit interaction between the amine nitrogen and palladium atom respectively. NMR spectroscopy between -40 and 25 degrees C shows that the di-NHC-amine ligand is flexible expressing C(s) symmetry and for 13 rotation of the mesityl groups is prevented. In the related C(1) complex [(kappa(3)-(tBu)CN(H)C(tBu))PdCl][Cl] (14) coordination of NHC moieties and amine nitrogen atom is observed between -40 and 25 degrees C. Reaction between 12-14 and two equivalents of AgBF(4) in acetonitrile gives the analogous complexes [trans-(kappa(2)-(tBu)CN(Bn)C(tBu))Pd(MeCN)(2)][BF(4)](2) (15), [trans-(kappa(2)-(Mes)CN(H)C(Mes))Pd(MeCN)(2)][BF(4)](2) (16) and [(kappa(3)-(tBu)CN(H)C(tBu))Pd(MeCN)][BF(4)](2) (17) indicating that ligand structure determines amine coordination. The single crystal X-ray structures of 12, 17 and two ligand imidazolium salt precursors (tBu)C(H)N(Bn)C(H)(tBu)][Cl](2) (2) and [(tBu)C(H)N(H)C(H)(tBu)][BPh(4)](2) (4) have been determined. Complexes 12-14 and 15-17 have been shown to be active precatalysts for Heck and hydroamination reactions respectively.