Synthesis and structure of dinuclear dimethylene- or 1,4-phenylene-linked bis(decamethyltitanoceneoxide) (Ti-III) complexes
2010
Abstract
The singly tucked-in titanocene [Ti(eta(5)-C(5)Me5())(eta(5):eta(1)-C5Me4CH2)] (1) reacts smoothly with ethylene glycol or hydroquinone to give bis(titanoceneoxide) (Ti-III) complexes [CH2OTi(eta(5)-C5Me5)(2)](2) (2) and [(eta(5)-C5Me5)(2)TiOC6H4OTi(eta(5)-C5Me5)(2)] (3) containing dimethylene and 1,4-phenylene link, respectively. EPR spectra of 2 in 2-methyltetrahydrofuran glass and 3 in toluene glass revealed that the unpaired d(1) electrons are in interaction to form triplet state molecules.
The Ti-Ti distance derived from the zero-field splittings D for the two conformations of 2 (7.42 angstrom and 7.66 angstrom) are in good agreement with the Ti-Ti distance of 7.2430(7) angstrom from the X-ray diffraction single-crystal analysis.