Exploration of Br⋯O halogen bonding interactions in dinuclear vanadium(V) complexes with Schiff base ligands. (1st September 2020)

• Record Type: Journal Article
• Authors: Thakur, Snehasish; Gil, Diego M.; Frontera, Antonio; Chattopadhyay, Shouvik
• Is Part Of: Polyhedron. Volume 187(2020)
• Publication Date: 2020-09-01
• Subjects: Vanadium(V) -- Schiff base -- Dinuclear -- DFT calculation -- Halogen bonding; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2020.114676
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: A novel μ2 -oxo bridged dinuclear vanadium(V) complex, (µ-O)2 [V(O)(L)]2, has been synthesized and characterized. Its structure has been confirmed by single crystal X-ray diffraction study. An infinite 1D chain has been generated which is actually governed by the Br⋯O halogen bond involving the oxygen atoms of the VO2 + unit as electron donor and the σ-hole at the bromine atom as electron acceptor. The interaction energies have been characterized energetically by using the Bader's quantum theory of "atoms in molecules" (QTAIM). The results have been compared with the energies of identical halogen bonding interactions in a structurally similar oxo-bridged dinuclear vanadium(V) complex. Abstract: An oxo-bridged dinuclear vanadium(V) complex, (µ-O)2 [V(O)(L)]2, [where HL = 2-((2-(methylamino)ethylimino)methyl)-4-bromo-6-methoxyphenol] has been synthesized and characterized by elemental and spectral analysis. Structure of the complex has been determined by single crystal X-ray diffraction study. The complex generates an infinite 1D chain governed by Br⋯O halogen bond involving the oxygen atoms of the VO2 + unit as electron donor and the σ-hole at the halogen as electron acceptor. The molecular electrostatic potential (MEP) surface of the complex has been computed, which indicates that the most electron rich part corresponds to the oxygen atoms of the VO2 + unit and the existence of a σ–hole (+9.4 kcal/mol) around Br atom, and therefore justifies the formation of a directional halogen bonding interaction. The interaction in the complex has also been characterized energetically by using the Bader's quantum theory of "atoms in molecules" (QTAIM). The contribution of the halogen bond is found to be ∼−6.3 kcal/mol, which is in the range of typical halogen bonds. The results have been compared with the energies of Br⋯O halogen bonding interactions in a structurally similar oxo-bridged dinuclear vanadium(V) complex.