A metallacyclic alkyl-amido carbene complex (MCAAC).

Area of Science:

• Organometallic Chemistry
• Coordination Chemistry
• Catalysis

Background:

• The C≡N moiety in redox-active metalloligands offers versatile reactivity.
• Hybrid ligands with multiple coordination sites are valuable in constructing complex metal architectures.

Purpose of the Study:

• To investigate the reactivity of the redox-active metalloligand [CpRu{κ(3)N(pz)-1}][PF6] (2) with an iridium precursor.
• To characterize the resulting bimetallic complex and elucidate its structural and electronic properties.

Main Methods:

• Nuclear Magnetic Resonance (NMR) spectroscopy
• X-ray crystallography
• Density Functional Theory (DFT) calculations
• Cyclic Voltammetry (CV)

Main Results:

• Formation of a bimetallic Ru(II)-Ir(III) complex, [CpRu{μ-1}Ir(cod)Cl2][PF6] (3), with a modified ligand.
• Discovery of an unprecedented metallacyclic alkyl-amido carbene (MCAAC) core structure coordinated to the Ir(III) center.
• CV studies revealed a Ru(II)/Ru(III) redox couple and stepwise reduction of Ir(III) to Ir(I).

Conclusions:

• The reaction successfully activated the C≡N bond, leading to a unique MCAAC structure.
• The electronic structure and oxidation states of the metals were investigated using electrochemical and computational methods.
• This work expands the scope of heterobimetallic complex synthesis and reactivity.