π-Bonded dithiolene complexes: synthesis, molecular structures, electrochemical behavior, and density functional...

Area of Science:

• Organometallic Chemistry
• Coordination Chemistry
• Materials Science

Background:

• o-Dithiobenzoquinone is an elusive intermediate due to its instability.
• Metal coordination can stabilize reactive organic species.
• Understanding the properties of such stabilized intermediates is crucial for developing new materials.

Purpose of the Study:

• To synthesize and characterize the first metal-stabilized o-dithiobenzoquinone.
• To explore the reactivity of this stabilized intermediate in forming novel binuclear complexes.
• To investigate the electronic and structural properties of the resulting compounds for potential applications.

Main Methods:

• Synthesis of metal-stabilized o-dithiobenzoquinone using iridium precursors.
• X-ray molecular structure determination of the synthesized compounds.
• Electrochemical studies to analyze redox properties.
• Density Functional Theory (DFT) calculations for electronic structure and spectral predictions.

Main Results:

• Successfully synthesized and characterized the first metal-stabilized o-dithiobenzoquinone, [Cp*Ir-o-(η(4)-C(6)H(4)S(2))].
• Developed a unique class of binuclear dithiolene compounds, [Cp*Ir(C(6)H(4)S(2))MCp*][OTf](2) (M = Rh, Ir), where the dithiolene acts as a bridging ligand.
• DFT calculations confirmed enhanced stability and electron reservoir properties of the bimetallic complexes.
• UV-vis spectra analysis indicated ligand-metal charge transfer transitions.

Conclusions:

• The metal stabilization of o-dithiobenzoquinone by π coordination yields a stable intermediate.
• The synthesized binuclear complexes exhibit unique bridging dithiolene structures and act as electron reservoirs.
• These findings open new avenues for the coordination chemistry of o-dithiobenzoquinone and its application in molecular materials.