Influence of the Ti-O-C Angle on the Oxygen-to-Titanium pi-Donation in [Cp-2*Ti(III)OR] Complexes

0351878 - ÚFCH JH 2011 RIV US eng J - Journal Article
Gyepes, R. - Varga, V. - Horáček, Michal - Kubišta, Jiří - Pinkas, Jiří - Mach, Karel
Influence of the Ti-O-C Angle on the Oxygen-to-Titanium pi-Donation in [Cp-2*Ti(III)OR] Complexes.
Organometallics. Roč. 29, č. 17 (2010), s. 3780-3789. ISSN 0276-7333. E-ISSN 1520-6041
R&D Projects: GA AV ČR IAA400400708; GA MŠMT(CZ) LC06070
Institutional research plan: CEZ:AV0Z40400503
Keywords : [Cp-2*Ti(III)OR] Complexes * oxygen * titanium
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 3.888, year: 2010

The constrained geometry alkoxide [Ti(III)(eta(5)-C5Me5){eta(5)-C5Me4CH2CMe2O-kappa O}] (2) and titanocene alcoholates [Cp*2TiOR] for R = 1-adamantyl (3) and pentafluorophenyl (4) were prepared by reacting acetone and the respective alcohols with the singly tucked-in titanocene [Ti(III)(eta(5)-C5Me5)(eta(5):eta(1)-C5Me4CH2)] (1) in order to add the simplest member to constrained geometry alkoxides 5 and 6 and to extend the series of [Cp*2TiOR] (R = Me (8), 'Bu (7), Ph (9), and H (10)) compounds for one of the most bulky and the most electron attracting substituent. The titanocene alkoxides with the alkoxy carbon atom tethered to one of the cyclopentadienyl ligands showing the crystallographic Ti-O-C angle close to 133 degrees are a suitable group of compounds to be compared with the [Cp*2TiOR] compounds, where the Ti-O-C angle is about 174 degrees for 3 and 7 and 180 degrees for 4.
Permanent Link: http://hdl.handle.net/11104/0191524