d-electron count, ion-pairing and diagonal twist angles in metallo-bis(dithiolene) complexes

Area of Science:

• Inorganic Chemistry
• Computational Chemistry
• Materials Science

Background:

• Late transition metals coordinated by dithiolene ligands are crucial in various chemical systems.
• Understanding their electronic structure and geometry is key to predicting their properties and reactivity.

Purpose of the Study:

• To perform electronic structure calculations for late transition metals with dithiolene ligands.
• To predict geometries of previously unreported Ni(I) species.
• To investigate the influence of ion pairing on the structures.

Main Methods:

• Density Functional Theory (DFT) calculations were employed.
• Calculations were performed for [M(mnt)2]n- compounds (M = Ni, Pd, Pt, Cu).
• Ion-pairing effects with various cations (alkali metals, tetra-alkyl ammonium) were simulated.

Main Results:

• Calculated structures align with existing data and predict novel Ni(I) geometries.
• The diagonal twist angle is dependent on the metal's d-electron count (0° to 90°).
• Ion-pairing energies vary with cation size and charge density, impacting geometry.

Conclusions:

• The study provides accurate structural predictions for metal-dithiolene complexes.
• Electronic structure and ion pairing are critical factors determining molecular geometry.
• Findings contribute to the understanding of coordination chemistry and materials design.