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Literary linguistics: Open Access research in English language

Strathprints makes available Open Access scholarly outputs by English Studies at Strathclyde. Particular research specialisms include literary linguistics, the study of literary texts using techniques drawn from linguistics and cognitive science.

The team also demonstrates research expertise in Renaissance studies, researching Renaissance literature, the history of ideas and language and cultural history. English hosts the Centre for Literature, Culture & Place which explores literature and its relationships with geography, space, landscape, travel, architecture, and the environment.

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Exposing the hidden complexity of stoichiometric and catalytic metathesis reactions by elucidation of Mg-Zn hybrids

Hevia, Eva and Chua, Jonathan Z. and Garcia-Alvarez, Pablo and Kennedy, Alan R. and McCall, Matthew D. (2010) Exposing the hidden complexity of stoichiometric and catalytic metathesis reactions by elucidation of Mg-Zn hybrids. Proceedings of the National Academy of Sciences, 107 (12). pp. 5294-5299. ISSN 0027-8424

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Abstract

Studying seemingly simple metathesis reactions between ZnCl2 and (BuMgCl)-Bu-t has, surprisingly, revealed a much more complex chemistry involving mixed magnesium-zinc compounds that could be regarded as Mg-Zn hybrids. Thus, the reaction of equimolar amounts of ZnCl2 and tBuMgCl reveals the formation of the unprecedented mixed Mg-Zn complex [(THF)(4)Mg(mu-Cl)(2)Zn(Bu-t)(Cl)] (1), as a result of the co-complexation of the two anticipated exchange products of the metathesis. This magnesium zincate adopts a contacted ion-pair structure, closely related to Knochel's pioneering "Turbo" Grignard reagents. Furthermore, a second coproduct identified in this reaction is the solvent-separated mixed magnesium-zinc chloride complex [{Mg(THF)(6)}(2+){Zn2Cl6}(2-)] (3) that critically diminishes the amount of ZnCl2 available for the intended metathesis reaction to take place. In another surprising result, when the reaction is carried out by using an excess of 3 M equivalents of the Grignard reagent (closer to the catalytic conditions employed by synthetic chemists), solvent-separated magnesium trialkyl zincate [{Mg2Cl3(THF)(6)}(+){Zn(Bu-t)(3)}(-)] (4) is obtained that can be viewed as a model for the active species involved in the increasingly important organic transformations of Grignard reagents catalysed by ZnCl2. Furthermore, preliminary reactivity studies reveal that complex 4 can be used as an effective new reagent for direct Zn-I exchange reactions that allow the preparation and structural identification of the magnesium tris(aryl) zincate [{Mg2Cl3(THF)(6)}(+){Zn(p-Tol)(3)}(-)] (5) that represents the first example of complete 3-fold activation of a zincate in a Zn-I exchange reaction which, in turn, can efficiently be used as a precursor for Negishi cross-coupling reactions.