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1, 8-Bis(hexamethyl-triamino-phosphazenyl)naphthalene, HMPN: A Superbasic Bisphosphazene "Proton Sponge" (CROSBI ID 115401)

Prilog u časopisu | izvorni znanstveni rad | međunarodna recenzija

Raab, Volker ; Gauchenova, Ekaterina ; Merkoulov, Alexei ; Harms, Klaus ; Sundermeyer, Jorg ; Kovačević, Borislav ; Maksić, Zvonimir 1, 8-Bis(hexamethyl-triamino-phosphazenyl)naphthalene, HMPN: A Superbasic Bisphosphazene "Proton Sponge" // Journal of the American Chemical Society, 127 (2005), 45; 15738-15743-x

Podaci o odgovornosti

Raab, Volker ; Gauchenova, Ekaterina ; Merkoulov, Alexei ; Harms, Klaus ; Sundermeyer, Jorg ; Kovačević, Borislav ; Maksić, Zvonimir

engleski

1, 8-Bis(hexamethyl-triamino-phosphazenyl)naphthalene, HMPN: A Superbasic Bisphosphazene "Proton Sponge"

It is shown that a combination of Schwesinger's phosphazene base concept and the idea of the disubstituted 1, 8-naphthalene spacer, first introduced by Alder in paradigmatic 1, 8-bis(dimethylamino)naphthalene (DMAN), yields a new superbase HMPN, which represents the up to date most basic representative of this class of "proton sponges" as evidenced by the theoretically estimated proton affinity PA = 274 kcal/mol and the measured pKBH+ (MeCN) 29.9 +0.2. HMPN is by nearly twelve orders of magnitude more basic than Alder's classical 1, 8-bis-(dimethylamino)naphthalene (DMAN). The title compound HMPN is prepared and fully characterized. The spatial structure of HMPN and its conjugate acid is determined by X-ray technique and theoretical DFT calculations. It is found that mono-protonated HMPN has an unsymmetrical intramolecular hydrogen bridge (IHB). This cooperative proton chelating effect renders the bis-phosphazene more basic than Schwesinger's set of "mono-dentate" P1 phosphazene bases. The density functional calculations are in good accordance with the experimental results, providing some complementary information. They conclusively show that the high basicity of HMPN is a consequence of the high energy content of the base in its initial neutral state and the intramolecular hydrogen bonding in the resulting conjugate acid with contributions to proton affinity of 14.1 and 9.5 kcal/mol, respectively.

Basicity; Peralkylated phosphazenes; Protonation; Proton sponge; Hydrogen bonding

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Podaci o izdanju

127 (45)

2005.

15738-15743-x

objavljeno

0002-7863

Povezanost rada

Kemija