Theoretical Study of Terminal Vanadium(V) Chalcogenido Complexes Bearing Chlorido and Methoxido Ligands

Samuel Tetteh,Ruphino Zugle

doi:10.1155/2017/6796321

Abstract

Solvent (methanol) coordinated vanadium(V) chalcogenido complexes bearing chlorido and methoxido ligands have been studied computationally by means of density functional (DFT) methods. The gas phase complexes were fully optimized using B3LYP/GEN functionals with 6-31+G⁎⁎ and LANL2DZ basis sets. The optimized complexes show distorted octahedral geometries around the central vanadium atom. The ligand pπ-vanadium dπ interactions were analyzed by natural bond order (NBO) and natural population analyses (NPA). These results show strong stabilization of the V=O bond as was further confirmed by the analyses of the frontier molecular orbitals (FMOs). Second-order perturbation analyses also revealed substantial delocalization of lone pair electrons from the oxido ligand into vacant non-Lewis (Rydberg) orbitals as compared to the sulfido and seleno analogues. These results show significant ligand-to-metal charge transfer (LMCT) interactions. Full interaction map (FIM) of the reference complex confirms hydrogen bond interactions involving the methanol (O-H) and the chlorido ligand.

Highlights

IntroductionChalcogens (Ch) (group of 16 elements) form one of the interesting groups of elements on the periodic table
Chalcogens (Ch) form one of the interesting groups of elements on the periodic table
C 2.147 1.724 2.250 2.426 2.331 2.317 101.17 96.06 171.94 162.52 96.27 83.61 96.22 77.22 manuscript, we report results of Cambridge Structural Database (CSD) searches for terminal vanadium(V) chalcogenido complexes bearing chlorido and methoxido ligands with coordinated methanol molecules

Summary

Introduction

Chalcogens (Ch) (group of 16 elements) form one of the interesting groups of elements on the periodic table. The study of complexes with terminal metal-oxo, sulfido, seleno, and related ligands is an interesting area of inorganic chemistry. This is partly because they are used as reagents and precatalysts [2, 3] for organic synthesis and as models for the active sites in heterogeneous processes. Interest in softer chalcogen (S and Se) containing complexes is rapidly increasing because of their potential application in bioinorganic and coordination chemistry [14] Covalent bonds involving these atoms have been shown to exhibit a localized region of positive potential which allows them to interact with electron donors to form typical noncovalent interactions similar to halogen bonds [15]. We have analyzed the full interaction map of the oxidovanadium complex using the Mercury program to identify possible contacts for intermolecular interactions and compared with data reported in the literature [17]

Methodology

Results and Discussion

C Occupancy

Conclusion