Lewis Acid Supported Nickel Nitrenoids.

Area of Science:

• Organometallic Chemistry
• Coordination Chemistry
• Materials Science

Background:

• Polynucleating ligands offer versatile platforms for constructing complex metal clusters.
• Understanding the electronic properties and reactivity of heterometallic clusters is crucial for catalysis and materials development.

Purpose of the Study:

• To synthesize and characterize novel heterometallic zinc-nickel clusters using a specific polynucleating ligand.
• To investigate the reactivity of these clusters, particularly their transformation into nitrenoid adducts.
• To elucidate the electronic structure and redox properties of the resulting nitrenoid species.

Main Methods:

• Metalation of the ligand ^F,tbs LH₆ with zinc precursors.
• Transmetalation with a nickel precursor to form a trinuclear cluster.
• Reductive activation and reaction with an azide to form a nitrenoid adduct.
• Characterization using EPR spectroscopy, cyclic voltammetry, X-ray absorption spectroscopy (XAS), and DFT calculations.

Main Results:

• Successful synthesis of dinuclear zinc, trinuclear heterometallic zinc-nickel, and subsequent nitrenoid adducts.
• The monovalent nickel center in the reduced cluster was successfully trapped by an adamantyl azide.
• EPR spectroscopy indicated a doublet ground state for the anionic nitrenoid cluster.
• Cyclic voltammetry revealed reversible redox events, and XAS/DFT studies provided insights into the nickel oxidation states.

Conclusions:

• The study demonstrates the utility of the ^F,tbs LH₆ ligand in constructing complex heterometallic clusters.
• The synthesized nitrenoid adducts exhibit interesting electronic and redox properties, with potential for further reactivity.
• The findings contribute to the understanding of metal-nitrene bonding and reactivity in polynuclear systems.