Synthesis and Reactivity of Discrete Europium(II) Hydride Complexes.

The bulky ß-diketiminate ligand frameworks [BDIDCHP]- and [BDIDipp/Ar]- (BDI=[HC{C(Me)2N-Dipp/Ar}2]- (Dipp=2,6-diisopropylphenyl (Dipp); Ar=2,6-dicyclohexylphyenyl (DCHP) or 2,4,6-tricyclohexylphyenyl (TCHP)) have been developed for the kinetic stabilisation of the first europium (II) hydride complexes, [(BDIDCHP)Eu(µ-H)]2, [(BDIDipp/DCHP)Eu(µ-H)]2 and [(BDIDipp/TCHP)Eu(µ-H)]2, respectively. These complexes represent the first step beyond the current lanthanide(II) hydrides that are all based on ytterbium. Tuning the steric profile of ß-diketiminate ligands from a symmetrical to unsymmetrical disposition, enhanced solubility and stability in the solution-state. This provides the first opportunity to study the structure and bonding of these novel Eu(II) hydride complexes crystallographically, spectroscopically and computationally, with their preliminary reactivity investigated.

Ytterbium (II) Hydride as a Powerful Multielectron Reductant.

A dimeric ß-diketiminato ytterbium(II) hydride affects both the two-electron aromatization of 1,3,5,7-cyclooctatetraene (COT) and the more challenging two-electron reduction of polyaromatic hydrocarbons, including naphthalene (E0 =-2.60 V). Confirmed by Density Functional Theory calculations, these reactions proceed via consecutive polarized Yb-H/C=C insertion and deprotonation steps to provide the respective ytterbium (II) inverse sandwich complexes and hydrogen gas. These observations highlight the ability of a simple ytterbium(II) hydride to act as a powerful two-electron reductant at room temperature without the necessity of an external electron to initiate the reaction and avoiding radicaloid intermediates.

Hydroarylation of olefins catalysed by a dimeric ytterbium(II) alkyl.

Although the nucleophilic alkylation of aromatics has recently been achieved with a variety of potent main group reagents, all of this reactivity is limited to a stoichiometric regime. We now report that the ytterbium(II) hydride, [BDIDippYbH]2 (BDIDipp = CH[C(CH3)NDipp]2, Dipp = 2,6-diisopropylphenyl), reacts with ethene and propene to provide the ytterbium(II) n-alkyls, [BDIDippYbR]2 (R = Et or Pr), both of which alkylate benzene at room temperature. Density functional theory (DFT) calculations indicate that this latter process operates through the nucleophilic (SN2) displacement of hydride, while the resultant regeneration of [BDIDippYbH]2 facilitates further reaction with ethene or propene and enables the direct catalytic (anti-Markovnikov) hydroarylation of both alkenes with a benzene C-H bond.

Providing care to refugees through mainstream general practice in the southern health region of New Zealand: a qualitative study of primary healthcare professionals' perspectives.

OBJECTIVE: To explore the perspectives of primary healthcare (PHC) professionals providing care to refugees through mainstream general practice. DESIGN: Qualitative exploratory design with semistructured interviews subjected to inductive thematic analysis. SETTING AND PARTICIPANTS: Nine general practices enrolled in the Dunedin Refugee Resettlement Programme, in New Zealand (NZ)'s southern health region. Participants included nine general practitioners and six practice nurses. RESULTS: Three analytical constructs were identified: relational engagement with refugees, refugee healthcare delivery and providers' professional role shaped by complexity. Building meaningful relational connections involved acknowledging refugees' journeys by getting to know them as people. This was instrumental for the development of an empathetic understanding of the complex human trajectories that characterise refugees' journeys to NZ. Participants encountered challenges in providing care to refugees with respect to time-limited consultations, variable use of interpreter services, fragmentation of care between agencies and need for improved health infrastructure to ensure a fluid interface between PHC, secondary care and community support services. The current business model of NZ general practice was perceived to interfere with value-driven care and discouraged tailoring of care to specific patient groups, raising concerns about the 'fit' of mainstream general practice to address the complex healthcare needs of refugees. Meeting the needs of refugees across the social determinants of health involved a lot of 'behind the scenes work' particularly in the absence of shared information systems and the lack of well-established referral pathways to connect refugees to services beyond the health sector. This led to providers feeling overwhelmed and uncertain about their ability to provide appropriate care to refugees. CONCLUSIONS: This study provides rich context-specific findings that enhance PHC responsiveness to the needs of refugees in NZ.

PEDOT-based composites as electrode materials for supercapacitors.

Poly (3, 4-ethylenedioxythiophene) (denoted PEDOT) already has a brief history of being used as an active material in supercapacitors. It has many advantages such as low-cost, flexibility, and good electrical conductivity and pseudocapacitance. However, the major drawback is low stability, which means an obvious capacitance drop after a certain number of charge-discharge cycles. Another disadvantage is its limited capacitance and this becomes an issue for industrial applications. To solve these problems, there are several approaches including the addition of conducting nanofillers to increase conductivity, and mixing or depositing metal oxide to enhance capacitance. Furthermore, expanding the surface area of PEDOT is one of the main methods to improve its performance in energy storage applications through special processes; for example using a three-dimensional substrate or preparing PEDOT aerogel through freeze drying. This paper reviews recent techniques and outcomes of PEDOT based composites for supercapacitors, as well as detailed calculations about capacitances. Finally, this paper outlines the new direction and recent challenges of PEDOT based composites for supercapacitor applications.