Intermolecular metallophilic interactions in palladium(II) chalcogenolate compounds – An experimental and theoretical study

The compounds [Pd2I2{Te((2,6-OCH3)2C6H3)}2(PCy3)2] (1), [Pd2I2{Te((2,6-OCH3)2C6H3)}2(PR2R')2]∙2CH3CN (2), [Pd2{Te((2,6-OCH3)2C6H3)}2(phen)2][Hg2Br6(phen)2] (3), [Pd2Cl2(TePh2)2(TePh)2] ∙ DMF (4), [Pd2(SePh)2(2,2′-bipy)2][HgBr4]∙2DMF (5), [Pd2(SePh)2-(phen)2][HgI4]∙5DMF (6), [Pd2{Te((2,6-OCH3)2C6H3)}2(phen)2][Hg2I6]-[Hg((2,6-OCH3)2C6H3)2] (7) containing [Pd2(µ-ER)2] core (E = Se, Te; R = aryl) were synthesized and characterized by IR spectroscopy, elemental analysis and X-ray crystallography. Intermolecular metallophilic interactions were evaluated through crystallographic studies combined with Density Functional Theory calculations. The structural stability of 4–7 were investigated taking in account the interactions E⋯E, Pd⋯Pd and Pd⋯Hg between [Pd2(µ-ER)2] cores.