1973 Volume 46 Issue 9 Pages 2662-2664
The charge transfer in acetonitrile-halogen complexes was examined by means of the nuclear quadrupole resonances resulting from the relevant nuclei. 14N NQR parameters (|e2Qq|=3.6000 MHz and η=0.0183) and 35Cl NQR parameters (|e2Qq|=107.44 and 108.50 MHz) were obtained for the acetonitrile-chlorine complex, whereas 14N NQR parameters (|e2Qq|=3.5439 MHz and η=0.0043) and a 81Br NQR parameter (|e2Qq|=640.52 MHz) were obtained for the acetonitrile-bromine complex. From these parameters, the charged states of the nitrogen, chlorine, and bromine atoms in these charge-transfer complexes were calculated by means of the Townes and Dailey theory. In the case of the acetonitrile-bromine complex, the charge loss at the nitrogen atom was not equal to the gain at the bromine atom, as long as the charge was assumed to be transferred only to the p-orbital of the latter. This discrepancy was explained by assuming some d-hybridization at the bromine atom. The charged states of the nitrogen atoms in these complexes were qualitatively in good agreement with the electron affinities of the chlorine and bromine molecules. Moreover, the temperature dependences of the 14N and 81Br nuclear quadrupole coupling constants in the acetonitrile-bromine complex were investigated in the range from −196 to −60 °C.
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