Molecular Hydrogen-Induced Carbon Chain Rearrangement in Cyclopentadienyl-Tethered Titanium(III) Permethyltitanocene Complexes

0520587 - ÚFCH JH 2021 RIV DE eng J - Journal Article
Pinkas, Jiří - Kubišta, Jiří - Gyepes, Robert - Mach, Karel - Horáček, Michal
Molecular Hydrogen-Induced Carbon Chain Rearrangement in Cyclopentadienyl-Tethered Titanium(III) Permethyltitanocene Complexes.
European Journal of Inorganic Chemistry. Roč. 2020, č. 1 (2020), s. 128-136. ISSN 1434-1948. E-ISSN 1099-0682
R&D Projects: GA ČR(CZ) GA17-13778S
Institutional support: RVO:61388955
Keywords : derivatives * activation * hydride * (eta-5-c5me5)2tir * coordination * thermolysis * reactivity * dichloride * insertion * ethene * Titanium
OECD category: Physical chemistry
Impact factor: 2.524, year: 2020
Method of publishing: Limited access

Dihydrogen added at atmospheric pressure and ambient temperature to cyclopentadienyl-tethered titanium(III) permethyltitanocene complexes induced the rearrangement of their tether [-CH2-C(Me)=C(R)-Ti], moving the double bond to the lateral position [-CH2-C(=CHR)-CH2-Ti]. The methyl substituent on the beta-carbon from the cyclopentadienyl ring is converted to methylene group binding the rearranged tether to titanium. Subsequent hydrogenation of compounds with [-CH2-C(=CHR)-CH2-Ti] R = Ph or SiMe3 gave saturated rearranged products whereas compound with [-CH2-C(=CMeCMe=CHMe)-CH2-Ti] resisted. Computational studies elucidated the reaction mechanism and established the catalytical role of molecular hydrogen. This type of isomerization can be conceived as a sigma-bond metathetic rearrangement leading to the formation of tethered complexes with decreased steric strain.
Permanent Link: http://hdl.handle.net/11104/0305243