Lantern-Type Divanadium Complexes with Bridging Ligands: Short Metal-Metal Bonds with High Multiple Bond Orders

Area of Science:

• Inorganic Chemistry
• Computational Chemistry
• Materials Science

Background:

• Divanadium complexes with V-V multiple bonds are known, particularly tetragonal paddlewheel structures.
• Understanding the electronic structure and bonding in these complexes is crucial for predicting their properties.

Purpose of the Study:

• To computationally investigate model divanadium complexes (V2Lx) with formamidinate, guanidinate, and carboxylate ligands.
• To determine the V-V formal bond orders and analyze the electronic structures across different spin states.
• To predict novel divanadium structures with short V-V multiple bonds.

Main Methods:

• Density Functional Theory (DFT) calculations were used to model tetragonal, trigonal, and digonal divanadium complexes.
• Molecular Orbital (MO) diagrams were employed to derive formal V-V bond orders.
• Analysis of V-V bond distances and comparison with experimental data.

Main Results:

• Several model divanadium complexes exhibit short V-V multiple bonds, with formal bond orders ranging from 3 to 4.
• Predicted short V≡V triple bonds and singlet ground states for tetragonal complexes match experimental observations.
• Digonal divanadium lanterns with very short V-V quadruple bonds are proposed as potential synthetic targets.

Conclusions:

• The study provides a comprehensive analysis of bonding in divanadium complexes, revealing a range of V-V multiple bond orders.
• Computational predictions offer valuable insights into the stability and properties of these complexes.
• The findings pave the way for the design and synthesis of new divanadium compounds with unique bonding characteristics.