Insertion of 1-t-butylpropyne into singly tucked-in permethyltitanocene. Synthesis, crystal structure of product and transition-state geometry
| Autor: | Karel Mach, Katarína Szarka, Jiří Kubišta, Róbert Gyepes, Michal Horáček, Jiří Pinkas |
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| Rok vydání: | 2018 |
| Předmět: |
Steric effects
chemistry.chemical_classification Reaction mechanism 010405 organic chemistry Chemistry Organic Chemistry Alkyne Crystal structure 010402 general chemistry 01 natural sciences 0104 chemical sciences Analytical Chemistry Inorganic Chemistry Metal Paramagnetism Crystallography visual_art Yield (chemistry) Structural isomer visual_art.visual_art_medium Spectroscopy |
| Zdroj: | Journal of Molecular Structure. 1167:180-186 |
| ISSN: | 0022-2860 |
| DOI: | 10.1016/j.molstruc.2018.04.071 |
| Popis: | The singly tucked-in titanocene [(η5-C5Me5)TiIII{η5:η1-C5Me4(CH2)}] (1) reacted with one equivalent of 1-tert-butylpropyne to yield the propenyl-tethered regioisomer [(η5-C5Me5)Ti(η5:η1-C5Me4CH2C(t-Bu) = κCMe)] (3). The exclusive formation of paramagnetic 3 was proved experimentally and steric reasons were clarified by DFT calculation of transition state which involves both π-systems on the alkyne for bonding interaction with the metal and with sp2 carbon atom of exomethylene group of 1. The obtained compound 3 is by 40 kJ/mol lower in energy than its hypothetical isomer having t-Bu group on Cα of the tether. |
| Databáze: | OpenAIRE |
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