Synthesis and Structure of 6-Aminofulvene-2-aldiminate Complexes

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• 作者：Alexander M. Willcocks ; Alexander Gilbank ; Stephen P. Richards ; Simon K. Brayshaw ; Andrew J. Kingsley ; Raj Odedra ; Andrew L. Johnson
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：February 7, 2011
• 年：2011
• 卷：50
• 期：3
• 页码：937-948
• 全文大小：1232K
• 年卷期：v.50,no.3(February 7, 2011)
• ISSN：1520-510X

文摘

We report here a synthetic route to bis(N,N鈥?aryl)-6-aminofulvene-2-aldimine (AFA) ligand systems, specifically Ph₂-AFAH and Dip₂-AFAH. The synthesis and structural characterization of a series of Cu(I) complexes [(Ph₂-AFA)Cu(CNPh)₂] (2), [(Ph₂-AFA)Cu(CNⁱPr)] (3), and [(Dip₂-AFA)Cu(CNⁱPr)] (4), from the reaction of the corresponding lithiated AFA systems with Cu鈭扖l derivatives are reported; notably in the case of [(Ph₂-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路路路蟺 interaction. The reactions of the AFA compounds Ph₂-AFAH and Dip₂-AFAH with ZnMe₂ and AlMe₃ have also been investigated, and the results of these reactions are described here.