4 resultados para ODD-ODD RE-174
em CentAUR: Central Archive University of Reading - UK
Resumo:
This paper presents a critical history of the concept of ‘structured deposition’. It examines the long-term development of this idea in archaeology, from its origins in the early 1980s through to the present day, looking at how it has been moulded and transformed. On the basis of this historical account, a number of problems are identified with the way that ‘structured deposition’ has generally been conceptualized and applied. It is suggested that the range of deposits described under a single banner as being ‘structured’ is unhelpfully broad, and that archaeologists have been too willing to view material culture patterning as intentionally produced – the result of symbolic or ritual action. It is also argued that the material signatures of ‘everyday’ practice have been undertheorized and all too often ignored. Ultimately, it is suggested that if we are ever to understand fully the archaeological signatures of past practice, it is vital to consider the ‘everyday’ as well as the ‘ritual’ processes which lie behind the patterns we uncover in the ground.
Resumo:
Sorace (2000, 2005) has claimed that while L2 learners can easily acquire properties of L2 narrow syntax they have significant difficulty with regard to interpretation and the discourse distribution of related properties, resulting in so-called residual optionality. However, there is no consensus as to what this difficulty indicates. Is it related to an insurmountable grammatical representational deficit (in the sense of representation deficit approaches; e.g. Beck 1998, Franceschina 2001, Hawkins 2005), is it due to cross-linguistic interference, or is it just a delay due to a greater complexity involved in the acquisition of interface-conditioned properties? In this article, I explore the L2 distribution of null and overt subject pronouns of English speaking learners of L2 Spanish. While intermediate learners clearly have knowledge of the syntax of Spanish null subjects, they do not have target-like pragmatic knowledge of their distribution with overt subjects. The present data demonstrate, however, that this difficulty is overcome at highly advanced stages of L2 development, thus suggesting that properties at the syntax-pragmatics interface are not destined for inevitable fossilization.
Resumo:
Electrochemical reduction of the triangular clusters [Os-3(CO)(10)(alpha-dimine)] (alpha-dimine = 2,2'-bipyridine (bpy), 2,2'-bipyrimidine (bpym)) and [Os-3(CO)(10)(mu-bpym) ReBr(CO)(3)] produces primarily the corresponding radical anions. Their stability is strongly determined by the pi acceptor ability of the reducible alpha-dimine ligand, which decreases in the order mu-bpym > bpym >> bpy. Along this series, increasing delocalisation of the odd electron density in the radical anion over the Os(alpha-dimine) chelate ring causes weakening of the axial (CO)(4)Os-Os(CO)(2)(alpha-dimine) bond and its facile cleavage for alpha-diimine = bpy. In contrast, the cluster radical anion is inherently stable for the bridging bpym ligand, the strongest pi-acceptor in the studied series. In the absence of the partial delocalisation of the unpaired electron over the Re( bpym) chelate bond, the Os-3-core of the radical anion remains intact only at low temperatures. Subsequent one-electron reduction of [Os-3(CO)(10)(bpym)](center dot-) at T = 223 K gives the open-triosmium core (= Os-3*) dianion, [Os-3*(CO)(10)(bpym)](2-). Its oxidation leads to the recovery of parent [Os-3(CO)(10)( bpym)]. At room temperature, [Os-3*( CO)(10)(bpym)](2-) is formed along a two-electron (ECE) reduction path. The chemical step (C) results in the formation of an open- core radical anion that is directly reducible at the cathodic potential of the parent cluster in the second electrochemical (E) step. In weakly coordinating tetrahydrofuran, [Os-3*(CO)(10)( bpym)](2-) rapidly attacks yet non- reduced parent cluster molecules, producing the relatively stable open- core dimer [Os-3*(CO)(10)(bpym)](2)(2-) featuring two open- triangle cluster moieties connected with an ( bpym) Os - Os( bpym) bond. In butyronitrile, [Os-3*( CO)(10)(bpym)](2-) is stabilised by the solvent and the dimer [Os-3*(CO)(10)(bpym)](2)(2-) is then mainly formed by reoxidation of the dianion on reverse potential scan. The more reactive cluster [Os-3(CO)(10)(bpy)] follows the same reduction path, as supported by spectroelectrochemical results and additional valuable evidence obtained from cyclic voltammetric scans. The ultimate process in the reduction mechanism is fragmentation of the cluster core triggered by the reduction of the dimer [Os-3*(CO)(10)(alpha- diimine)](2)(2-). The products formed are [Os-2(CO)(8)](2-) and {Os(CO)(2)(alpha- diimine)}(2). The latter dinuclear fragments constitute a linear polymeric chain [Os( CO)(2)(alpha-dimine)] n that is further reducible at the alpha-dimine ligands. For alpha-dimine = bpy, the charged polymer is capable of reducing carbon dioxide. The electrochemical opening of the triosmium core in the [Os-3( CO)(10)(alpha-dimine)] clusters exhibits several common features with their photochemistry. The same Os-alpha-dimine bond dissociates in both cases but the intimate mechanisms are different.