Homocoupling of C₁ building blocks by a heterometallic Mg-Al complex

Area of Science:

• Organometallic Chemistry
• Catalysis
• Synthetic Chemistry

Background:

• Homologation reactions are crucial for extending carbon chains in organic synthesis.
• Metal hydrides are versatile reagents in catalysis and organic transformations.
• Selective functionalization of small carbon molecules (C1 building blocks) remains a significant challenge.

Purpose of the Study:

• To report a novel heterometallic magnesium-aluminium hydride complex.
• To investigate the selective homologation of C1 building blocks (CO and CNXyl) using this complex.
• To explore the formation of new carbon-carbon and carbon-heteroatom bonds.

Main Methods:

• Synthesis and characterization of a heterometallic magnesium-aluminium hydride complex.
• Reaction of the complex with carbon monoxide (CO).
• Reaction of the complex with an organic cyanide (CNXyl).

Main Results:

• Selective homologation of CO into deltate or ethynediolate motifs, influenced by ligand sterics.
• Formation of a novel metalated ethene diamidolate ligand via C-C bond formation and hydride migration with CNXyl.
• Demonstration of distinct reactivity pathways for CO and CNXyl.

Conclusions:

• The heterometallic complex exhibits selective reactivity towards different C1 building blocks.
• The steric environment around the magnesium center dictates the outcome of CO homologation.
• A new synthetic route to a metalated ethene diamidolate ligand has been established.