The Bond N -Cl. A Spectroscopic (35Cl-NQR, IR) Investigation

Abstract

Abstract Chlorine bound to nitrogen is an interesting oxidizing agent in aqueous, partial aqueous and non-aqueous media. One can assume that the oxidizing action of the chlorine depends on the polarization of the Cl atom in the bond N -Cl which will depend on the electron distribution in the ligands R and R″ of the configuration R -NCl -CO -R″. 17 compounds were synthesized with R = substituted phenyl radical C6H5-y Xy, X = Cl, NO2, R″ = CH2Cl. The 35Cl NQR frequencies are observed in the range 52 to 54 MHz (T = 77 K) for the Cl(N) 34 to 37 MHz for the phenyl chlorines and the CH2Cl group. Their temperature dependence was followed up to 300 K. Therefrom the assignment of the resonance to certain Cl-atoms in the molecules is possible. Generally, the substitution of a negative substituent X (Cl, NO2) in the phenyl ring raises the resonance frequencies; the influence of the CH2Cl group on the N -Cl bond is weak. Strong is the influence of the carbonyl group on the N -C l bond. The IR group frequencies ν(C = O) are found in the range 1680 ≤ ν (C = O)/ cm−1≤ 1717, shifted up by ≤ 20 cm−1 compared to the corresponding acetamide R ⎯ NH ⎯CO ⎯ R″. Influence of the phenyl ring substitution on ν (C = O) does not follow a simple law of inductive effect. Also a correlation between the vibration frequencies of the N ⎯ Cl group and the phenyl group substitution is not found.