Density functional studies revealed that nucleophilic silyl radicals are able to mask as electrophiles by cyclizing with high preference onto the more electron-rich nitrogen atom of imine C=N double bonds. This remarkable behavior is a result of a combination of SOMO-pi and lone pair (LP)-sigma* interactions during the reaction. If the LP is not available due to steric reasons, attack of the Si-radical occurs with slight preference at the carbon atom. This indicates that "dual orbital" interactions are directing the regioselectivity of silyl radical cyclizations.