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Insertion of 1-t-butylpropyne into singly tucked-in permethyltitanocene. Synthesis, crystal structure of product and transition-state geometry
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SYSNO ASEP 0492089 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Insertion of 1-t-butylpropyne into singly tucked-in permethyltitanocene. Synthesis, crystal structure of product and transition-state geometry Author(s) Pinkas, Jiří (UFCH-W) RID, ORCID
Mach, Karel (UFCH-W) ORCID, RID
Kubišta, Jiří (UFCH-W) RID, ORCID
Horáček, Michal (UFCH-W) RID, ORCID
Szarka, K. (SK)
Gyepes, R. (SK)Source Title Journal of Molecular Structure. - : Elsevier - ISSN 0022-2860
Roč. 1167, SEP 2018 (2018), s. 180-186Number of pages 7 s. Language eng - English Country NL - Netherlands Keywords internal alkynes ; reduction ; complexes ; density ; ethene ; Titanocene Subject RIV CF - Physical ; Theoretical Chemistry OECD category Physical chemistry R&D Projects GA17-13778S GA ČR - Czech Science Foundation (CSF) Institutional support UFCH-W - RVO:61388955 UT WOS 000435052300022 EID SCOPUS 85047431176 DOI 10.1016/j.molstruc.2018.04.071 Annotation 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. Workplace J. Heyrovsky Institute of Physical Chemistry Contact Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Year of Publishing 2019
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