Eigenschaften und thermische Reaktionen von Komplexen der Arendiazoniumsalze mit Kronenethern

Properties and Thermal Reactions from Complexes of Arene Diazonium Salts with Crown Ethers In contrast to 18-crown-6, the substituted crown ethers Benzo-18-crown-6, Dibenzo-18-crown-6, and Naphtho-18-crown-6 form in solution complexes with p-CH₃ C₆H₄ N₂⁺BF₄-characterized by a broad charge transfer absorption up to 550 nm. The formation constants lg K_c are 2,32 2,16 and 1,44 for Benzo-, Dibenzo-, and Naphtho-18-crown-6, respectively. Formation enthalpy ΔH = −7,5 kJ/mol and entropy ΔS = +18 J/K mol are measured in the case of p-Cl C₆H₄ N₂⁺BF₄⁻ and Dibenzo-18-crown-6 (20°). K_c depends on substituents in the arene ring of the diazonium salt; ϱ = +0,8. Thermal dediazoniation in the presence of Crown ethers results in high yields of the corresponding arene. This is explained by a fast radical chain reaction between the diazonium salt and the polyether (Meerwein-Reduction).