Calculation of geometric parameters of macrocyclic metal chelates formed by template synthesis in tertiary systems M(II) ion-ethanedithioamide-formaldehyde-ammonia

• Published in: Russian journal of inorganic chemistry Vol. 56; no. 2; pp. 223 - 231
• Main Authors: Chachkov, D. V, Mikhailov, O. V
• Format: Journal Article
• Language: English
• Published: Dordrecht Dordrecht : SP MAIK Nauka/Interperiodica 2011; SP MAIK Nauka/Interperiodica
• Subjects: Bonding; Chelates; Chemistry; Chemistry and Materials Science; Crosslinking; Density functional theory; Gaussian; Inorganic Chemistry; Macrocyclic compounds; Mathematical analysis; Packages; Synthesis; Theoretical Inorganic Chemistry; Dithio; Membered Ring; Coordination Core; Chelate Ring; Template Synthesis
• ISSN: 0036-0236; 1531-8613
• DOI: 10.1134/S0036023611020057

The geometric parameters of macrotricyclic Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes with 2,8-dithio-3,5,7-triazanonanedithioamide-1,9 with the (N,N,S,S) coordination of the chelant donor centers (formed by template synthesis in the M(II)-ethanedithioamide-formaldehyde-ammonia system) have been calculated by the hybrid B3LYP density functional theory method with the use of the 6-31G(d) basis set and the Gaussian 98 program package. The bond lengths and bond angles in the complexes with the MN₂S₂ coordination core have been reported. Calculations demonstrated that in none of the complexes are the five-membered chelate rings planar and that these rings in the Zn(II) complex are significantly different. For all M(II) ions under consideration, an additional six-membered chelate ring resulting from template cross-linking is turned at a rather large angle to the two five-membered rings and this ring itself is nonplanar.