In carbon and silicon tetrahalide compounds, the experimental 13C and 29Si NMR chemical-shift values are known to increase or decrease on increasing the overall sum of the ionic radii of the bonded halides S(rh) (normal and inverse halogen dependence (NHD and IHD, respectively)). Herein, we extrapolate the main factors responsible for such NMR chemical shifts. Intriguingly, we found a characteristic value for the overall sum of the Pauling electronegativities of the bonded halides S(ch), which works as a triggering factor to determine the transition from the NHD to IHD. Below this S(ch) value, the chemical shift of the central atom was strictly related to only the S(rh) value, thus producing a NHD trend. Conversely, above this value, the chemical shift of the central atom was dependent on both the S(rh) and S(ch) values, thus producing a IHD trend. A simple model, in which the effect of the S(ch) value on 13C and 29Si NMR chemical shifts is related to an apparent increase in the S(rh) value, is deduced.
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