Structural Changes in the Macrocycles of Tetrathioand Dithiodioxo-Substituted 1,8-Dioxa-3,6,10,13-tetraazacyclotetradecane Caused by Complexation with 3d M(II) Ions according to Quantum-Chemical DFT Calculation

Abstract

The bond angles in the macrocycles of tetrathio- and dioxodithio-substituted 1,8-dioxa-3,6,10,13-tetraazacyclotetradecanes and their Cr(II), Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes with the (NNNN) coordination of the ligand donor sites, formed upon the complexation in the ternary systems M(II)–ethanedithioamide H₂N–C(=S)–C(=S)–NH₂ (thiocarbamoylmethanamide H₂N–C(=S)–C(=O)–NH₂)–formaldehyde H₂C(=O) in gelatin-immobilized matrix implants have been calculated by the DFT OPBE/TZVP method with the Gaussian 09 program package. It has been stated that, depending on the nature of M(II) and macrocyclic ligand, the complexation can lead to both the decrease and the increase in the degree of macrocycle distortion (quantatively characterized as the degree of deviation of the macrocycle from coplanarity).