Reactions of directly related tellurium and selenium heterocycic compunds with triiron dodecacarbonyl

The reactions of directly related tellurium and selenium heterocyclic compounds with triiron dodecacarbonyl are described. The reaction of 2-telluraphthalide, C8H8OTe with [Fe3(CO)12 gave [Fe{C6H4(CH2)Te}(CO)3]2, (1). An iron atom has inserted into the telluracyclic ring, and it is probable that one co-ordinated CO ligand arises from the initially organic carbonyl group. X-ray analysis of compound (1) showed that the compound has a Fe2Te2 core, which is achieved by dimerisation. The reaction of telluraphthalic anhydride, C8H402Te with [Fe3(CO)12] gave a known, but unexpected, organic phthalide product, C8H602, which was confirmed by X-ray crystallography. Selenaphthalic anhydride,  C8H4O2Se gave intractable products on reaction with [Fe3(CO)12], 2-selenaphthalide, C8H6OSe, on reaction with [Fe3(CO)12] gave a major product [Fe2{C6H4(CH2)Se}(CO)6], (2) and a minor product [Fe3{C6H4(CH2)Se}(CO)8], (3) which is an intermediate in the formation of (2). X-ray analysis of (2) shows that compound (2) is very similar to (1) except that the 18 electron rule is satisfied by co-ordination of a Fe(CO)3 moiety, rather than dimerisation. Compound (3), also studied by X-ray crystallography, differs from (2) mainly in the addition of an Fe(CO)2 moiety. Telluraphtbalic anhydride, C8H402Te, and selenaphthalic anhydride, C8H402Se, are both monoclinic and crystallise in space group P21/n. 2-Selenaphthalide, C8H402Se, is also monoclinic, space group P21/C. The reactions of the following compounds (l,3-dihydrobenzo[c]selenophene, 1,3,7,9-tetrahydrobenzo[1,2c; 4,5c'] ditellurophene, dibenzoselenophene, phenoxselenine, 3, 5-naphtho-1-telluracyclohexane and 3,5-naphtho-1-selenacyclohexane) with [Fe3lCO)12] are reported. It is unfortunate that the above compounds do not react under the conditions employed; this may be due to differing degrees of ring strain. 1,8-bis(bromomethyl)naphthalene, C12H10Br2 is monoclinic and crystallises in space group C2/c. 1,1-diiodo-3,5-naphthotelluracyclohexane, C12H10TeI2 and 3,5-naphtho-l-telluracyclohexane, C12H10Te are monoclinic and crystallise in space group P21/c. 3,5-naphtho-l-selenacyclohexane, C12H10Se and 2,2,8,8-tetraiodo-1,3,7,9-tetrahydrobenzo[1,2c;4,5c']ditellurophene are also monoclinic, space group P21/a. The syntheses of intramolecular stabilised organo-tellurium and selenium compounds are reported, having a general formula of REX (where R = phenylazophenyl; E = Se, Te; X = electronegative group, for example C1, Br or I). The crystal structures of R'TeBr, RTeI, RSeCI, RSeCI/I and RSeI (where R = phenylazophenyl) are reported. The tellurium containing X-ray structures are triclinic and have a space group P-1. The selenium containing X-ray structures are monoclinic with space group P21/n. The inclusion of nitrogen in selenium heterocycles provides access to an entirely new area of organometallic chemistry. The reaction of 2-methylbenzoselenazole with [Fe3(CO)12] gave [Fe2{C6H4(NCH2CH3)Se}(CO)6]. The reactions of 2-(methyltelluro)benzanilide or 2-(methylseleno)benzanilide with [Fe3(CO)12] gave reaction products [Fe2(μTeMe)2(CO)6] and [Fe2 (μ-SeMe)2(CO)6] respectively, which were confmned by X-ray crystallography. The use of Mossbauer spectroscopy on the products obtained from the reactions of heterocyclic compounds with [Fe3(CO)12] can give useful information, for example the number of iron sites and the environments of these iron sites within the products.

Submission for the degree of Doctor of Philosophy by published work at Aston University

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Professions, class and society:solicitors in 19th century Birmingham

The thesis provides an analysis of an occupation in the process of making itself a profession. The solicitors' profession in Birmingham underwent a great many changes during the 19th century against a background of industrialisation and urbanisation. The solicitors' conception of their status and role, in the face of these challenges, had implications for successful strategies of professionalisation. The increased prestige and power of the profession, and especially its elite, are examined in their social context rather than in terms of a technical process, or educational and organisational change. The thesis argues that -the profession's social relationships and broad concerns were significant in establishing solicitors as "professional men". In particular these are related to the profession's efforts to gain control of markets for legal services and increase social status. In the course of achieving these aims a concept of profession and a self-image were articulated by solicitors in order to persuade society and the state of the legitimacy of their claims. The concept of the gentlemanly professional was of critical importance in this instance. The successful creation of a provincial professional "community" by the end of the 19th century rested principally on a social and moral conception of professionalism rather than one which stressed specialised training and knowledge, professional organisations and credentials.

Activity and affect:repeated within-participant assessment in people after joint replacement surgery

Objective: Between-participant research has shown that high negative affectivity predicts greater activity limitations and vice versa. This study examined both between- and within-participant associations of negative and positive affectivity with activity levels using ecological momentary assessment. Method: Participants were 25 people who had undergone joint replacement surgery 12 months previously. Participants made multiple reports of their activity and positive and negative affectivity over a single day using, a computerized diary. Activity was also objectively recorded using an activity monitor. The following day, participants made a self-report of their activity over the measurement day and general positive and negative affectivity levels were recorded. Results: Higher self-reported walking time over the whole measurement day was associated with higher general positive affectivity but not negative affectivity. However, using ecological momentary assessment, higher diary reports of negative affectivity predicted increased activity levels while positive affectivity neither predicted nor was predicted by activity. Conclusion: These findings demonstrate the importance of within-participant methodology in detecting subtle and immediate effects of individuals' mood on behavior that may differ from findings investigating between-participant effects over longer time periods.