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Insertion of 1-t-butylpropyne into singly tucked-in permethyltitanocene. Synthesis, crystal structure of product and transition-state geometry
- 1.0492089 - ÚFCH JH 2019 RIV NL eng J - Journal Article
Pinkas, Jiří - Mach, Karel - Kubišta, Jiří - Horáček, Michal - Szarka, K. - Gyepes, R.
Insertion of 1-t-butylpropyne into singly tucked-in permethyltitanocene. Synthesis, crystal structure of product and transition-state geometry.
Journal of Molecular Structure. Roč. 1167, SEP 2018 (2018), s. 180-186. ISSN 0022-2860. E-ISSN 1872-8014
R&D Projects: GA ČR(CZ) GA17-13778S
Institutional support: RVO:61388955
Keywords : internal alkynes * reduction * complexes * density * ethene * Titanocene
OECD category: Physical chemistry
Impact factor: 2.120, year: 2018
The singly tucked-in titanocene [(eta(5)-C5Me5)Ti-III{eta(5):eta(1)-C5Me4(CH2)}] (1) reacted with one equivalent of 1-tert-butylpropyne to yield the propenyl-tethered regioisomer [(eta(5)-C5Me5)Ti(eta(5):eta(1)-C5Me4CH2C(t-Bu) = kappa CMe)] (3). The exclusive formation of paramagnetic 3 was proved experimentally and steric reasons were clarified by DFT calculation of transition state which involves both 7r-systems on the alkyne for bonding interaction with the metal and with sp(2) carbon atom of exomethylene group of I. The obtained compound 3 is by 40 kJ/mol lower in energy than its hypothetical isomer having t-Bu group on C-alpha of the tether. (C) 2018 Elsevier B.V. All rights reserved.
Permanent Link: http://hdl.handle.net/11104/0285654
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Number of the records: 1