Wewnętrzna solwatacja a reakcje przeniesienia protonu w fazie gazowej dla związków azotowych

• Autorzy: Raczyńska E.D.

Warianty tytułu

EN

Internal solvation and proton transfer reactions in gas phase for nitrogen compounds

• Języki publikacji: PL

Abstrakty

EN

Intramolecular hydrogen bonding which can be formed in the neutral or ionic forms of polyfunctional compounds strongly influences the simple proton-transfer reactions and tautomeric equilibria in the gas phase. This effect, called internal solvation increases the proton affinities of nitrogen ligands, such as proton sponges with a rigid structure, and diamines, amidinamines, bipyridines and amidinazines with a flexible conformation by 20-100 kJ/mol in comparison to monofunctional or model compounds. In consequence diamines and amidinamines belong to superbases (PA>1000 kJ/mol). In aqueous solutions, only proton sponges are strong bases. Due to strong steric effects, water molecules cannot open the ionic NźźźH-N+ bridge in the proton sponges. Bidentate nitrogen ligands with a flexible conformation behave in solution similarly as monofunctional derivatives. External solvation by water molecules eliminates the NźźźH-N+ bridge, changes conformation of the monocation (from cyclic to linear), reduces polarizability of the chain, and thus decreases the basicity. For tautomerizing azoles, the internal solvation changes the pK(T) values by more than 2 pK(T) units in comparison to derivatives without this interaction. Application of the Taft and Topsom equation to series of 4(5)-substituted imidazoles indicates that the internal solvation in the gas phase has similar influence on the transmission of substituent effects as the external solvation in water.

Słowa kluczowe

PL

reakcja przeniesienia protonu; wewnętrzna solwatacja; gąbki protonowe; ligandy azotowe

• Wydawca: Polskie Towarzystwo Chemiczne
• Czasopismo: Wiadomości Chemiczne
• Rocznik: 2000
• Tom: [Z] 54, 1-2
• Strony: 67--86
• Opis fizyczny: tab., bibliogr. 78 poz.

Twórcy

autor

Raczyńska E.D.

• Wydział Chemii Uniwersytetu im. Adama Mickiewicza ul. Grunwaldzka 6, 60-780 Poznań

• Katedra Chemii, Szkoła Główna Gospodarstwa Wiejskiego ul. Rakowiecka 26/30, 02-528 Warszawa

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Uwagi

PL

Opracowanie rekordu ze środków MEiN, umowa nr SONP/SP/546092/2022 w ramach programu "Społeczna odpowiedzialność nauki" - moduł: Popularyzacja nauki i promocja sportu (2022-2023).