Reactions of CuCl2 with 1-(N-indolylmethyl)and 1-(N-carbazolylmethyl)silatranes (L) afforded new complexes CuCl2•L. Quantum chemical calculations of these complexes and a CuII complex with 1-(N-pyrrolylmethyl)silatrane showed that the Cu atom is coordinated to both the equatorial O atom of the silatranyl group and the π-system of the ligandś heterocycle.