Synthesis and structure of 6-aminofulvene-2-aldiminate complexes |
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Authors: | Willcocks Alexander M Gilbank Alexander Richards Stephen P Brayshaw Simon K Kingsley Andrew J Odedra Raj Johnson Andrew L |
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Institution: | Department of Chemistry, University of Bath, Bath, United Kingdom. |
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Abstract: | We report here a synthetic route to bis(N,N'-aryl)-6-aminofulvene-2-aldimine (AFA) ligand systems, specifically Ph(2)-AFAH and Dip(2)-AFAH. The synthesis and structural characterization of a series of Cu(I) complexes (Ph(2)-AFA)Cu(CNPh)(2)] (2), (Ph(2)-AFA)Cu(CN(i)Pr)] (3), and (Dip(2)-AFA)Cu(CN(i)Pr)] (4), from the reaction of the corresponding lithiated AFA systems with Cu-Cl derivatives are reported; notably in the case of (Ph(2)-AFA)Cu(CNPh)(2)] studies have revealed the existence of two structural isomers (2a and 2b), both of which can be isolated and structurally characterized. Density functional theory (DFT) calculations suggest that the two crystal forms are comparatively close in energy, and geometry optimization reveals a convergence of these two forms to a geometry that more closely resembles the solid-state structure of isomer 2b, having a CH···π interaction. The reactions of the AFA compounds Ph(2)-AFAH and Dip(2)-AFAH with ZnMe(2) and AlMe(3) have also been investigated, and the results of these reactions are described here. |
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