Copper(I) complexes of N-centered aliphatic tripodal trithioether ligands - Adjustment of complex geometry by variation of spacer lengths

摘要

A series of novel aliphatic tripodal trithioether ligands 4-6 differing in the lengths of the alkyl chains between central nitrogen atom and sulfur donor function has been synthesized. The neutral ligands 4-6 react with copper(I) under formation of the mononuclear complexes 7-9 featuring exclusive coordination of the metal center by the tertiary amine and the three thioether donor functions of the tripodal ligand. Molecular structures of 7 and 9 show a direct influence of the spacer lengths between central and terminal donor functions on the geometry of the tetracoordinated complex cations. Substitution of one ethylene by a propylene spacer leads to a larger bite angle between the amine and thioether donor functions and effects a tetrahedral distortion for the complex cation in 7. For the copper(I) compound 9 with a ligand possessing exclusively propylene spacers this effect is increased leading to a tetrahedral geometry of the complex cation.