Hydrazine complexes with formic acid formed in the N2H4—HCOOH—HCOO− system in the presence of KOBut—DMSO superbase: a quantum chemical study

• Published in: Russian chemical bulletin Vol. 73; no. 8; pp. 2191 - 2198
• Main Authors: Orel, V. B., Gnatovskiy, G. R., Vitkovskaya, N. M.
• Format: Journal Article
• Language: English
• Published: New York Springer US 2024; Springer Nature B.V
• Subjects: Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Continuum modeling; Formic acid; Full Articles; Hydrazines; Inorganic Chemistry; Organic Chemistry; Potassium; Quantum chemistry; Solvation; formic acid; quantum chemical calculations; hydrazine; dimethyl sulfoxide; formylhydrazine; potassium formate
• ISSN: 1066-5285; 1573-9171
• DOI: 10.1007/s11172-024-4340-5

Hydrazine complexes with formic acid, free formate ion, and a potassium formate complex 5DMSO · K + HCOO − formed in the system N 2 H 4 —HCOOH—K + HCOO − — DMSO were studied. The possibility for hydrazine formylation to occur was assessed. According to calculations, a [N 2 H 6 (HCOO) 3 ] − complex is formed in the system in question. The calculated kinetic and thermodynamic characteristics suggest that hydrazine formylation can occur in this complex. The reaction is reversible; as a consequence, the reaction medium can contain both the [N 2 H 6 (HCOO) 3 ] − complex and formylhydrazine. All calculations were carried out using the B2PLYP-D2/6-311+G**//B3LYP/6-31+G* approach with inclusion of solvation effects in terms of the IEFPCM continuum model with DMSO as solvent and with explicit inclusion of the nearest solvation shell of the potassium cation (five DMSO molecules).