The trans influence in unsymmetrical pincer palladacycles: an experimental and computational study

A library of unsymmetrical SCN pincer palladacycles, [ClPd{2-pyr-6-(RSCH2)C6H3}], R = Et, Pr, Ph, p-MePh, and p-MeOPh, pyr = pyridine, has been synthesized via C–H bond activation, and used, along with PCN and N’CN unsymmetrical pincer palladacycles previously synthesized by the authors, to determine the extent to which the trans influence is exhibited in unsymmetrical pincer palladacycles. The trans influence is quantified by analysis of structural changes in the X-ray crystal and density functional theory (DFT) optimized structures and a topological analysis of the electron density using quantum theory of atoms in molecules (QTAIM) to determine the strength of the Pd-donor atom interaction. It is found that the trans influence is controlled by the nature of the donor atom and although the substituents on the donor-ligand affect the Pd-donor atom interaction through the varied electronic and steric constraints, they do not influence the bonding of the ligand trans to it. The data indicate that the strength of the trans influence is P > S > N. Furthermore, the synthetic route to the family of SCN pincer palladacycles presented demonstrates the potential of late stage derivitization for the effective synthesis of ligands towards unsymmetrical pincer palladacycles

Acting, interacting, enacting: Representing medical practice in theatre performance

This study followed the rehearsals of a 2014 Copenhagen theatre production of Margaret Edson’s play WIT. The play depicts the palliative care provision of a woman diagnosed with advanced ovarian cancer, with an important theme of the narrative centering around the dehumanizing practices that result from professional medical treatment of the body, rather than of the person. I adopt an interaction analytic approach to investigate how theatre practitioners develop representations of interaction in clinical environments. The article introduces one practice from the theatre rehearsal setting – doing notes – which forms a framework within which members reflect on their performances, and discuss possible modifications to be taken up on later occasions. This is argued to be a useful practice that may prove beneficial to other professional settings, such as in heathcare provision

Acting, interacting, enacting: Representing medical practice in theatre performance

This study followed the rehearsals of a 2014 Copenhagen theatre production of Margaret Edson’s play WIT. The play depicts the palliative care provision of a woman diagnosed with advanced ovarian cancer, with an important theme of the narrative centering around the dehumanizing practices that result from professional medical treatment of the body, rather than of the person. I adopt an interaction analytic approach to investigate how theatre practitioners develop representations of interaction in clinical environments. The article introduces one practice from the theatre rehearsal setting – doing notes – which forms a framework within which members reflect on their performances, and discuss possible modifications to be taken up on later occasions. This is argued to be a useful practice that may prove beneficial to other professional settings, such as in heathcare provision

Barriers, challenges and facilitators of implementing the UNICEF UK Baby Friendly Initiative (BFI) in a maternity organisation: a qualitative study of the experiences of maternity staff

Title: Barriers, challenges and facilitators to successfully implementing the UNICEF UK Baby Friendly Initiative (BFI) in a maternity organisation: a qualitative study of the experiences of maternity staff. Background: Breastfeeding is widely recognised for its health benefits for both infants and mothers, however it faces significant socio-cultural barriers, particularly in industrialised societies. Many women encounter barriers and challenges that hinder their ability to effectively breastfeed their infants. In 1994 UNICEF UK introduced the UK national accreditation programme named The Baby Friendly Initiative (BFI). It has recognition in numerous government policy documents across all four UK nations. This accreditation programme was developed to assist both hospital and community-based services, such as maternity and neonatal units, health visiting services and children’s centres with promoting close and loving relationships between parents and their infants and supports infant feeding practices. With published evidence demonstrating the benefits of breastfeeding and the UK government making it a requirement for all maternity units to be accredited to BFI standards, it highlighted a need for research in a local maternity that had their accreditation status removed by UNICEF UK. That was the stimulus which provided the rationale for this study. Methods: Maternity and neonatal staff participated in face to face and online semi-structured interviews. A qualitative, case study approach involving reflexive thematic analysis identified barriers, challenges and facilitators to successfully implementing the BFI. Findings: Four themes were developed from the research findings, these are staff training, staff knowledge, time and responsibility for providing infant feeding support. Organisational factors such as lack of staff education, lack of resources and confusion regarding whose role it is to support infant feeding; individual factors such as personal and professional feeding experiences and socio-political factors such as attitudes of women and relatives and the influence of the UK media all present barriers and facilitators to successful implementation of the BFI within the maternity unit. Conclusion: There is a strong formula feeding culture in the UK which requires commitment of staff and the community to change. Derogatory terms are still being applied to proponents of breastfeeding which is compounded by the UK media messaging. Successful implementation of the BFI relies on midwifery management support and funding for the process. One of the main strengths of this work is the applicability of the findings and recommendations to NHS trusts who wish to successfully implement or maintain the UNICEF UK BFI within their maternity service. What has been contributed to the field of knowledge is highlighting the requirement for managerial belief, support and funding for the BFI, alongside supporting a BFI lead role within their maternity service who is supported by passionate, proactive and educated staff. Transparency of the accreditation process and job expectations of all staff is essential

The nature of the bonding in symmetrical pincer palladacycles

The accuracy of DFT-optimised geometries of the symmetrical pincer palladacycles PdNCN and PdSCS, [ClPd{2,6- Me2NCH2)2C6H3}] and [ClPd{2,6-(MeSCH2)2C6H3}] respectively, has been evaluated by investigating the performance of eight commonly used density functionals with four combinations of basis set, in reproducing their X-ray crystal structures. It was found that whilst the ωB97XD functional performed best over all, the PBE and TPSS functionals performed best when considering the palladium coordination geometry. The role of the donor atom in the stability and reactivity of the symmetric palladacycles, PdYCY, Y = N, S, or P, has been determined using Bader’s Atoms in Molecules method to elucidate the nature of the bonding, and using a model formation reaction, which involves the C–H activation of the pincer ligand YCY by PdCl2. The calculations reveal distinct differences in the bond strength and nature of the interaction of Pd with the donor atoms Y, which support differences in the thermodynamic stability of the palladacycles

Identities at odds: embedded and implicit language policing in the internationalized workplace

This study offers an interaction analytic account of how linguistic identities in internationalized workplaces in Denmark are indexed against members' institutional positions in particular interactional contexts. Where language policy may not be explicitly articulated between members, it is still embedded in how participants micro-manage their interactions and implicit in how members display orientations to deviance, in the case of encountering others in the workplace whose language repertoires or preferences do not meet with expectation pertaining to the institutional position they hold. The study uses recordings of naturally occurring interaction in different international workplace settings and argues for greater attention to be paid to the actual language-policy practices in international workplace settings, as an entry point into developing a more nuanced understanding of the practices through which professional identities are brought about, affirmed or contested, and the linguistic considerations that are implicated in this

Rationalization of the mechanism of in situ Pd(0) formation for cross-coupling reactions from novel unsymmetrical pincer palladacycles using DFT calculations

Density functional theory (DFT) is used to determine the mechanism for Pd(0) generation from pincer palladacycle pre-catalysts. The elucidated mechanisms comprise two key steps, transmetallation and reductive elimination. It is found that the presence of a base in the pre-catalyst activation step serves to significantly lower the Gibbs free energy barrier of the transmetallation step and the Gibbs free energy of the overall pre-catalyst activation. The DFT results are used to rationalize the catalytic activity of a number of pincer palladacycles in the Suzuki-Miyaura coupling of sterically demanding and electronically deactivated aryl bromides with 2-tolyboronic acid. A strong correlation exists between the Gibbs free energy barrier of the transmetallation step and/or overall pre-catalyst activation energy and the percentage conversions of the Suzuki- Miyaura coupling in the presence of the novel pre-catalysts. The data presented suggest that the slow, controlled release of the “true, active catalyst,” Pd(0), from the pincer palladacycle pre-catalysts provides the optimum reaction conditions and may be achieved by a high transmetallation energy barrier or overall pre-catalyst activation energy or both