Naslov
Design of Superbasic Guanidines: The Role of Multiple Intramolecular Hydrogen Bonds

Autori
Barić, Danijela ; Dragičević, Ivan ; Kovačević, Borislav

Izvornik
Journal of organic chemistry (0022-3263) 78 (2013), 8; 4075-4082

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
superbases; guanidines; intramolecular hydrogen bonds; DFT

Sažetak
New organic superbases have been designed using the concept of multiple intramolecular hydrogen bonds. Substituents capable of forming strong intramolecular H-bonds were selected on the basis of the energy of stabilization that occurs upon the formation of a complex between N, N', N"-trimethylguanidine and small model molecules. The proton affinities and the corresponding pKa values in acetonitrile of the new superbases are examined by Density Functional Theory (DFT). It is shown that N, N', N"-substitution of guanidine with appropriate substituents results in new organic superbases with gas phase proton affinities between 286 and 293 kcal/mol, thus being 15 to 20 kcal/mol more basic than parental superbase N, N', N"-tris[(3-dimethylamino)propyl]-guanidine (tris-DMPG), whereas estimated pKa values in acetonitrile range between 29.5 and 33.2.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA