Molecular structures of macrotricyclic 4d M(II) chelates with the (NNNN)-donor ligand 2,7-dithio-3,6-diazaoctadiene-3,5-dithioamide-1,8 according to quantum-chemical density functional theory calculations

Abstract

The thermodynamic and geometric parameters of the molecular structures of macrotricyclic Mo(II), Ru(II), Rh(II), Pd(II), Ag(II), and Cd(II) complexes with the tetradentate ligand 2,7-dithio-3,6-diazaoctadiene-3,5-dithioamide-1,8 with the (NNNN) coordination of the donor centers have been calculated by the hybrid density functional theory (DFT) method in the OPBE/TZVPQZP approximation with the use of the Gaussian09 program package. The Pd(II), Ag(II), and Cd(II) complexes are exactly planar, the Tc(II) and Rh(II) complexes exhibit slight deviations from coplanarity, while the Mo(II) and Ru(II) complexes have rather significant deviations. The five-membered chelate rings in the complexes are either strictly planar or deviate slightly (no more than by 5°) from coplanarity.