RESUMO
In alkyllithium chemistry the highest reactivity has historically been linked to the smallest degree of aggregation possible. Since tert-butyllithium is known to form a monomer in tetrahydrofuran solution, using just stoichiometric amounts of the lewis base to selectively form a dimeric species seemed irrational. In this study, we showed a considerable increase of the reactivity of t-BuLi when using stoichiometric amounts of THF in the non-polar solvent n-pentane in order to enable the deprotonation of simple methyl silanes and other low C-H-acidic substrates. In this context, we were able to obtain the corresponding aggregates of t-BuLi with the ligand THF in suspension and as crystalline solids and investigate them by single crystal X-ray structural analysis, inâ situ FTIR spectroscopy and quantum chemical calculations. Furthermore, we were able to explain the enhanced reactivity of t-BuLi with stoichiometric amounts of THF on the basis of structural features of the bridged dimer obtained under these conditions. With these findings, we present a new target in the aggregation of alkyllithium reagents: the selectively formed "frustrated" aggregates!
RESUMO
The metalation of N,N-dimethylaminomethylferrocene in THF by the superbasic mixture of n BuLi/KOt Bu proceeds readily at low temperatures to afford a bimetallic Li2 K2 aggregate containing ferrocenyl anions and tert-butoxide. Starting from an enantiomerically enriched ortho-lithiated aminomethylferrocene, an enantiomerically pure superbase can be prepared. The molecular compound exhibits superbasic behavior deprotonating N,N-dimethylbenzylamine in the α-position and is also capable of deprotonating toluene. Quantum chemical calculations provide insight into the role of the bridging THF molecule to the possible substrate-reagent interaction. In addition, a benzylpotassium alkoxide adduct gives a closer look into the corresponding reaction site of the Lochmann-Schlosser base that is reported herein.
Assuntos
Compostos Organometálicos , Indicadores e Reagentes , Compostos Organometálicos/química , Lítio/química , Tolueno , ÂnionsRESUMO
The crystal structure of the title 2:1 mol-ecular complex between 2-(allyl-thio)-pyridine and 1,2,4,5-tetra-fluoro-3,6-di-iodo-benzene, C6F4I2·2C8H9NS, at 100â K has been determined in the monoclinic space group P21/c. The most noteworthy characteristic of the complex is the halogen bond between iodine and the pyridine ring with a short Nâ¯I contact [2.8628â (12)â Å]. The Hirshfeld surface analysis shows that the hydrogenâ¯hydrogen contacts dominate the crystal packing with a contribution of 32.1%.
RESUMO
The title compound N,N,N',N'-tetra-methyl-ethanedi-amine, C6H16N2, is a bidentate amine ligand commonly used in organolithium chemistry for deaggregation. Crystals were grown at 243â K from n-pentane solution. The complete mol-ecule is generated by a crystallographic center of symmetry and the conformation of the di-amine is anti-periplanar. To investigate the inter-molecular inter-actions, a Hirshfeld surface analysis was performed. It showed that Hâ¯H (van der Waals) inter-actions dominate with a contact percentage of 92.3%.