Nashrieh Shimi va Mohandesi Shimi Iran

Nashrieh Shimi va Mohandesi Shimi Iran

Theoretical Study on the Strength and Nature of Metal-Dichalcogenolate Bond in Homoleptic Metal Bis(Dichalcogenolene) Complexes [M(C3E5)2]2– (E=S, Se; M=Zn(II), Cd(II), Hg(II))

Document Type : Research Article

Authors
Elnaz Arzhangi
Yasin Gholiee
Department of Applied Chemistry, Faculty of Science, Malayer University, Malayer, I.R. IRAN
Abstract
In this paper, a theoretical study on the homoleptic metal bis(dichalcogenolene) complexes [M(C3E5)2]2– (E=S, Se; M=Zn(II), Cd(II), Hg(II)) have been done, at BP86/def2-TZVP and M06/def2-TZVP levels of theory. After optimization of all structures and observing a very good structural agreement with available experimental data, the different types of interaction energies between the fragments as well as the total interaction energies in all studied complexes were calculated. The results of the calculated total interaction energies show the following trend for studied dianionic complexes: [ZnL2]2‒ > [HgL2]2‒ > [CdL2]2‒. Moreover, the calculated total interaction energies are decreased by changing the E atom from sulfur to selenium. The results of the energy decomposition analysis, at BP86-D3/TZ2P(ZORA) level of theory, show that the orbital interactions have considerably less contribution to the total attractive interactions compared to electrostatic interactions. However, the contribution of orbital interactions, in an opposite trend with the interaction energies, is increased by changing the chalcogen atom from sulfur to selenium.
Keywords
Bis(dichalcogenolate) complexes
Interaction Energy
Nature of Bond
Energy Decomposition Analysis

Subjects

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