Bis(2-pyridyl)diselenoethers with the general formula (2-PySe)2(CH2)n [n = 1, 3 and 4] react with CuI, AgNO3, CuCl2·2H2O and CoCl2·6H2O resulting in the formation of products with molecular or multidimensional structures depending on the stoichiometry of the reactants and the conditions applied. The versatility of this class of selenium-containing ligands is demonstrated with the synthesis and structural characterization of six new complexes of the composition [CuCl2{(2-PySe)2CH2}]n (1), [Cu4I4{(2-PySe)2CH2}2] (2), [CuCl2{(2-PySe)2(CH2)3}2] (3), [CoCl2{(2-PySe)2(CH2)3}]n (4), [Ag{(2-PySe)2–(CH2)}3]n(NO3)n (5) and [CuCl2{(2-PySe)2(CH2)4}]n (6), respectively. The Cu(I) complex (2) was tested as catalyst in cross-coupling reactions.
