Alkyloxy- and aryloxy-titanocenes: Synthesis, solid-state structure and cyclic voltammetric studies

Alkyloxy- and aryloxy-functionalized titanocenes of type [Ti](Cl)(OR) (R = Me (2), CH2PPh2 (3), CH2Fc (4), C6H5 (5), C6H4-4-CN (6), C6H4-4-NO2 (7), C6H4-4-Me (8), C6H4-4-OMe (9), C6H4-4-C(O)Me (10), C6H4-4-CO2Me (11), C6H4-3-NO2 (12); [Ti] = (η5-C5H4SiMe3)2Ti; Fc = (η5-C5H4)(η5-C5H5)Fe) were synthesized by the reaction of [Ti]Cl2 (1) with ROH in a 1:1 molar ratio and in presence of Et2NH. Diaryloxy-titanocenes (e.g., [Ti](OC6H4-4-NO2)2 (13)) are accessible, when the ratio of 1 and ROH is changed to 1:2. This synthesis methodology also allowed the preparation of dinuclear complexes of composition ([Ti](Cl))2(μ-OC6H4O) (14) and ([Ti](Cl)(μ-OC6H4-4))2 (15) by the reaction of 1 with hydroquinone or 1,1′-dihydroxybiphenyl in a 2:1 stoichiometry.Cyclic voltammetric studies show the characteristic [Ti(IV)/Ti(III)] reductions. It was found that the potentials of the alkyloxy titanocenes 2–4 do not differ, while for the aryloxy-titanocenes 5–15 the reduction potentials correlate linearly with the σp/m Hammett substituent constants showing a strong influence of the substituents on the electron density at titanium.The structures of titanocenes 4, 5, 9, and 11–13 in the solid state are reported. Typical for these organometallic sandwich compounds is a distorted tetrahedral coordination geometry around titanium with D1–Ti–D2 angles (D1, D2 = centroids of the cyclopentadienyl ligands) of ca. 130 °. In comparison to FcCH2O-functionalized 4, for the aryloxy-titanocenes 5, 9, and 11–13 a significant larger Ti–O–C angle was found confirming electronic interactions between the titanium atom and the appropriate aryl group.

Graphical abstractThe synthesis and reactivity of diverse alkyloxy- and aryloxy-titanocene chlorides, bis(aryloxy) titanocenes, ([Ti]Cl)2(μ-OC6H4O) and ([Ti](Cl)(μ-OC6H4-4))2 is described. The structures of six samples in the solid state are reported. The electrochemical behavior of these molecules is discussed.Figure optionsDownload full-size imageDownload as PowerPoint slide