Iridium(VII)-Corrole Terminal Carbides Should Exist as Stable Compounds
Jeanet Conradie1,2, Abraham B Alemayehu1, Abhik Ghosh1
1Department of Chemistry, UiT The Arctic University of Norway, N-9037 Tromsø, Norway.
ACS Organic & Inorganic Au
|March 1, 2023
Summary
Stable iridium(VII)-corrole terminal carbide complexes are predicted by scalar-relativistic DFT calculations. These novel iridium carbide compounds are expected to be isolable and stable under ambient conditions.
Area of Science:
- Inorganic Chemistry
- Computational Chemistry
- Quantum Chemistry
Background:
- Corrole ligands are versatile macrocycles capable of stabilizing high oxidation states in metal complexes.
- Terminal carbide ligands are rare and highly reactive, posing synthetic challenges.
Purpose of the Study:
- To theoretically investigate the stability and properties of iridium(VII)-corrole terminal carbide complexes.
- To explore the feasibility of synthesizing and isolating novel iridium carbide species.
Main Methods:
- Scalar-relativistic Density Functional Theory (DFT) calculations were employed.
- Multiple exchange-correlation functionals (e.g., OLYP) and large basis sets (e.g., STO-TZ2P) were utilized.
Main Results:
- Calculations predict a stable iridium(VII)-corrole terminal carbide structure with a short Ir-C bond (1.69 Å).
- The complex exhibits a moderately domed macrocycle, low electron affinity (∼1.1 eV), and a significant singlet-triplet gap (∼1.8 eV).
- Results showed essential invariance across different exchange-correlation functionals.
Conclusions:
- Iridium(VII)-corrole terminal carbide complexes are predicted to be stable and isolable under ambient conditions.
- These findings open avenues for the synthesis of unprecedented organometallic compounds.
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