Synthesis, crystal structure and electrochemistry of tetrahedral mono-β-diketonato titanocenyl complexes
作者:Elizabeth Erasmus、Jeanet Conradie、Alfred Muller、Jannie C. Swarts
DOI:10.1016/j.ica.2006.11.010
日期:2007.5
The synthesis of a variety of tetrahedral beta-diketonato titanium(IV) complexes of the type [(C5H5)(2)Ti(CH3COCHCOR)]+ClO4- with R = CF3, OCH3, C6H5, CH3 and Fc is described. The Ti-III/T-IV couples and the Fc/Fc(+) couple exhibited chemically and electrochemically reversible cyclic voltammetric behaviour. The formal reduction potential of the Ti-III/IV couple increased as the group electronegativity of the R group of the beta-diketonato ligand increased. Bulk electrolysis showed that one electron was transferred in the Ti-III/IV couple and one electron in the ferrocenyl/ferrocenium redox couple in the ligand. The crystal structure for the R = OCH3 complex showed that this P-keto-ester binds through the carbonyl oxygen of the ester group and not the ether oxygen. (C) 2006 Elsevier B.V. All rights reserved.