Eta3-sandwich-like complexes based on the smallest polynitrogen ring

Area of Science:

• Inorganic Chemistry
• Computational Chemistry
• Materials Science

Background:

• Polynitrogen chemistry has advanced significantly, yet N(3)-based compounds remain elusive.
• The simplest polynitrogen ring, N(3), has not been incorporated into stable molecular structures.

Purpose of the Study:

• To report the first successful computational design of N(3)-based polynitrogen compounds.
• To investigate the structural, electronic, and bonding properties of these novel species.

Main Methods:

• Density functional theory (DFT) calculations were employed for the design and analysis.
• Structural, charge distribution, and orbital analyses were performed.

Main Results:

• Successfully designed several N(3)-based compounds, including [N(3)NiN(3)](2-), [N(3)M(CO)(2)N(3)](q), [N(3)M(CO)(3)](q), and [N(3)MCp](q).
• Computational analysis revealed a triplet cyclic-(3)N(3)(-) unit, not cyclic-(1)N(3)(+).
• The unpaired spins in cyclic-(3)N(3)(-) actively participate in bonding with transition metals (Ni, Fe, Co, Mn).

Conclusions:

• The diradical-like cyclic-(3)N(3)(-) unit is a novel building block for polynitrogen chemistry.
• Designed compounds exhibit kinetic stability due to significant energy barriers for conversion and dissociation.
• Proposed experimental routes for N(3)Co(CO)(3) and await experimental verification.