Abstract
Abstract Reaction of trimethylsilylcyanide with titanium (IV) chloride occurs readily at room temperature. Mono-adduct formation occurs initially, followed by substitution of chloride by cyanide under more forcing conditions. By choosing appropriate reaction conditions, it has been possible to isolate a series of products of composition, TiCl4−n(CNn · (CH3)3SiCN (n = 0, 1, 2, 3). The products are believed to possess dimeric (n = 0, 1) or polymeric (n = 2, 3) structures, containing approximately octahedrally coordinated titanium atoms. Attempts to remove the coordinated molecules from these products by thermal decomposition have proved unsuccessful, although adducts of composition TiCl2(CN)2·(CH3CN)1.5 and TiCl2(CN)2·(CH3CN)0.5 have been produced from ligand exchange reactions with acetonitrile. The titanium (IV) bromide analogue of the unsubstituted adduct, i.e. [TiBr4·(CH3)3SiCN]2, has also been isolated but attempts to produce substituted titanium-cyanide complexes from titanium (IV) bromide or titanium (IV) iodide yield intractable mixtures of products.
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