First Study of the Thermal and Storage Stability of Arenediazonium Triflates Comparing to 4-Nitrobenzenediazonium Tosylate and Tetrafluoroborate by Calorimetric Methods

Abstract

Herein, for the first time, using isothermal flow calorimetry and differential scanning calorimetry (DSC)/thermal gravimetric analysis (TGA), we have determined the thermal decomposition energies for the number of solid arenediazonium triflates comparing to 4-nitrobenzene tosylate and 4-nitrobenzentetrafluoroborate. The kinetics of thermal decomposition, activation energies, and half-lives of the studied diazonium salts (DSs) were found. Using gas chromatography–mass spectrometry (MS) and liquid chromatography–MS, we have elucidated the products formed during thermolysis of the investigated DSs. By density functional theory quantum chemical calculations at the B3LYP/aug-cc-pVDZ level of theory, we simulated the thermodynamics of decomposition reactions proceeding via substitution of the diazonium group by corresponding nucleophiles. The method applied predicted the decomposition energies of all the studied compounds fairly precise, except for 2-nitrobenzene diazonium triflate. It has been found that 4-nitrobenzene diazonium triflate has increased storage stability under normal conditions comparing to the corresponding tosylate and tetrafluoroborate. The experimental and theoretical results demonstrated that comparing to DSC/TGA, isothermal flow calorimetry more adequately reflects the energetics of the thermal decomposition of DSs and their storage stability under normal conditions.

Grafting of Diazonium Salts on Surfaces: Application to Biosensors

“…The many reviews (Table 1) published for the construction of biosensors using diazonium salts as anchoring molecules testified to the interest in this method [7,8,[65][66][67][68][69]. The objective of this section is to carry out a review of biosensors using the electroreduction of diazonium salts structured by analyte type, each of them having specificities in terms of sensor typology and expected analytical performances.…”

Development of Latent Fingerprints via Aryldiazonium Tetrachloroaurate Salts on Copper Surfaces: An XPS Study

“…In recent years, aryldiazonium salts of tosylates, triflates, and tetrachloroaurate , series emerged as very stable and safe, as they could be stored at room temperature; they are even stable up to 80–100 °C; triflates could be stable after decades just like it has been claimed . This is a tremendous progress in the chemistry of diazonium salts.…”

“…In the recent years, aryldiazonium salts of tosylates, 25, triflates 26 and tetrachloroaurate 27,28 series emerged as very stable and safe, as they could be stored at room temperature; they are even stable up to 80-100 °C, triflates could be stable after decades as has just been claimed. 26 This is a tremendous progress in the chemistry of diazonium salts. Whilst most of diazonium salts are soluble in aqueous media and react with surfaces to form surface-aryl interfacial bonds, what makes the tetrachloroaurate series unique is that the reduction of the salt affects both the diazonium cation and AuCl 4 -.…”

Surface functionalization of nanomaterials by aryl diazonium salts for biomedical sciences

“…Explosions have been reported during their use; [48], [49] ) should be used as counter ions as they provide stable diazonium ions. [50] In aprotic solvents, diazonium salts are stable in acetonitrile (ACN) which is most often used for surface grafting. In aqueous solution, the diazonium salts present two pK a corresponding to the formation of diazohydroxide (Ar-N=N-OH) and diazoates (Ar-N=N-O-) as the pH increases.…”