Patterns in supraicosahedral metallacarboranes

Chapter one gives an introduction into heteroborane chemistry focussing on supraicosahedral metallacarboranes. Chapter two describes the first examples of untethered 4,1,2-MC2B10 13-vertex metallacarboranes prepared by polyhedral expansion of a tethered carborane precursor. C,C'-dimethyl 4,1,6-MC2B10 compounds were afforded as co-products of the reactions. In contrast to the analogous 1,2- to 1,6- carborane rearrangement, experimental observations and DFT calculations reveal that 4,1,2- to 4,1,6- metallacarborane isomerisation does not occur under standard laboratory conditions. Chapter three constitutes the most extensive examination to date of the relationship between ligand orientational preference and bond strength in supraicosahedral molecules. A structural study of nine 13-vertex indenyl cobaltacarboranes supplemented by DFT calculations on models of related naphthalene ferracarboranes provided information on the relative trans influences of facial cage atoms. Chapter four describes the synthesis and characterisation of 1,14,2,9- and 1,14,2,10-M2C2B10 14-vertex cobaltacarboranes. The first unambiguous confirmation of 1,14,2,9-M2C2B10 architecture from crystallographic studies and supporting spectroscopic data is presented. A series of six asymmetric, 14-vertex, bicapped hexagonal antiprismatic bimetallacarboranes with 1,8/13,2,x-Co2C2B10 atom arrangements, thought to be the results of direct electrophilic insertion reactions, are reported in chapter five. A detailed analysis of crystallographic data resulted in the identification of cage C atom positions in all six isomers. Chapter six contains experimental procedures and characterisation details for all the new compounds reported herein. Crystallographic data is listed in appendices A and B (CD) along with structure solution and refinement details

How to Make 8,1,2-closo-MC2B9 Metallacarboranes

Three examples of the rare 8,1,2-closo-MC2B9 isomeric form of an icosahedral metallacarborane have been isolated as unexpected trace products in reactions. Seeking to understand how these were formed we considered both the nature of the reactions that were being undertaken and the nature of the coproducts. This led us to propose a mechanism for the formation of the 8,1,2-closo-MC2B9 species. The mechanism was then tested, leading to the first deliberate synthesis of an example of this isomer. Thus, deboronation of 4-(η-C5H5)-4,1,8-closo-CoC2B10H12 selectively removes the B5 vertex to yield the dianion [nido-(η-C5H5)CoC2B9H11]2−, oxidative closure of which affords 8-(η-C5H5)-8,1,2-closo-CoC2B9H11 in moderate yield

A chronological review of Scotland's policies and strategic priorities for implementation of pharmacy-related technologies.

National strategies across the world have highlighted the need for improving technology in healthcare. This study aims to summarise the goals and intentions of the Scottish Government and evaluate implementation

Chelating N-heterocyclic carbene-carboranes offer flexible ligand coordination to IrIII, RhIII and RuII: effect of ligand cyclometallation in catalytic transfer hydrogenation

Imidazolium salts linked by an ethyl tether to closo-dicarbadodecaboranes were reacted with [IrCp*Cl2]2, [RhCp*Cl2]2 or [Ru(p-cymene)Cl2]2 in the presence of Ag2O to prepare complexes of the type [MCp*(NHC)Cl2] (M = Ir, Rh; NHC = N-heterocyclic carbene) or [Ru(p-cymene)(NHC)Cl2]. When the NHC contained an N-tBu substituent, C–H activation of the tBu and subsequent alkyl coordination was observed at Ir. Coordination of the closo-dicarbadodecaborane moiety to Ir was possible to give 7-membered metallacycles, coordinated through the carbenic carbon of the NHC and either a carbon atom or a boron atom of the carborane. Examination of the Ir complexes in the transfer hydrogenation of acetophenone to 1-phenylethanol reveals that cyclometallation of the carborane moiety is important for catalytic efficacy, indicating a bifunctional mechanism and involvement of the dicarbadodecaborane anion

Evaluation of educational needs in patients with diabetes mellitus in respect of medication use in Austria

Effective control of diabetes mellitus type 1 (DM1) and type 2 (DM2) can reduce the development and progression of diabetic complications. Therefore, patient education should be considered as an integral part of diabetes management. Objective The aim of the study was to assess DM patients’ perception of knowledge for their medication and attitude towards self management and pharmacist’s role. Setting The study was conducted at the diabetes out-patient clinic at the Vienna General Hospital (AKH), Division of Endocrinology and Metabolism, Department of Internal Medicine III, Austria. The study was a cross sectional survey using patient data from a validated patient questionnaire and medical records. Medical records were evaluated by applying a medication assessment tool. Main outcome measure To assess the quality of diabetes self management the following outcome measures are considered: HbA1c levels, pre- and post-prandial blood glucose levels, prevention of acute episodes of hypo- and hyperglycaemia, reduction of macrovascular risk factors, short term quality of life, adverse effects and treatment tolerance. Results The present study comprised 225 patients with DM1 and 201 patients with DM2, respectively. In comparison to DM2 patients, cardio- and cerebrovascular diseases were diagnosed very rarely in patients with DM1. The risk for these diseases was higher in patients with other factors of the metabolic syndrome, in addition. Overall, 118 of these patients participated in the questionnaire. The level of positive response on diabetes self-care and knowledge with respect to medication for the prevention of diabetes complications, glycaemic control, and treatment goals in diabetes was 81.8 %. The comparison of patients’ perceptions of diabetes self-care and knowledge showed differences among subgroups. Higher perceived knowledge and selfcare apparently was associated with DM1. Additional findings of this study indicate that patients do not expect community pharmacists to be integrated in a multidisciplinary diabetes care team. Although the level of positive response was found to be high there is still a minority of patients whose level of comprehension appears to be insufficient. Intense pharmaceutical care including patients’ education within a multidisciplinary team could contribute to improvements in those patients

Development of novel approaches to demonstrate the quality of drug therapy use

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