Exchange interaction of Mo with 3d and 4d metals in complexes with dithiooxamide: a theoretical modeling

• Published in: Russian chemical bulletin 2022, Vol.71 (4), p.819-823
• Main Authors: Aldoshin, S. M., Bozhenko, K. V., Utenyshev, A. N.
• Format: Article
• Language: English
• Subjects: Brief Communications; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Coordination compounds; Coupling (molecular); Electronic structure; Inorganic Chemistry; Iron; Metal ions; Molecular structure; Organic Chemistry; Oxidation; Palladium; Quantum chemistry; Transition metals; Valence
• ISSN: 1066-5285; 1573-9171
• DOI: 10.1007/s11172-022-3483-5

Quantum chemical calculations of the molecular and electronic structure of the complexes [(L) 2 M1 3+ (L)M2 2+ (L) 2 ] 5− (M1 3+ is the Mo ion in the oxidation state +3; M2 2+ is the 3d and 4d transition-metal (Fe, Ru, Rh, Pd) ion in the oxidation state +2; and L is the dithiooxamide ligand) were carried out to search for pairs of metals corresponding to the maximum value of the exchange coupling constant J . Molecular structure calculations of the complexes were performed in the B3LYP/LANL2DZ approximation while the J constants were obtained from B3LYP/TZV calculations. It was shown that replacement of 3d transition-metal ions in the oxidation state +2 by 4d transition-metal ions in the oxidation state +2 leads to higher J values. It was established that the J values change in parallel with the difference between the total spin density on the M1 3+ and M2 2+ metal ions in the complexes and in the isolated M1 3+ and M2 2+ ions.