Synthesis and structure of dinuclear dimethylene- or 1,4-phenylene-linked bis(decamethyltitanoceneoxide) (Ti) complexes |
| |
| Authors: | Michal Horá ?ek,Ivana Cí sa?ová ,Ji?í Pinkas |
| |
| Affiliation: | a J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejškova 3, 182 23 Prague 8, Czech Republic
b Department of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 2030, 128 40 Prague 2, Czech Republic |
| |
| Abstract: | The singly tucked-in titanocene [Ti(η5-C5Me5)(η5:η1-C5Me4CH2)] (1) reacts smoothly with ethylene glycol or hydroquinone to give bis(titanoceneoxide) (TiIII) complexes [CH2OTi(η5-C5Me5)2]2 (2) and [(η5-C5Me5)2TiOC6H4OTi(η5-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 d1 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 Å and 7.66 Å) are in good agreement with the Ti-Ti distance of 7.2430(7) Å from the X-ray diffraction single-crystal analysis. For 3, however, the Ti-Ti distance derived from D (7.65 Å) is by 1.47 Å shorter than the crystallographic distance of 9.1230(8) Å that indicates an enhancement of the through-space dipole-dipole interaction due to the presence of a conjugated quinonide link. |
| |
| Keywords: | Titanium Titanocene Dinuclear complexes Dioxocarbyl links Triplet state ESR spectra |
| 本文献已被 ScienceDirect 等数据库收录！ |
|
