Work

Homocoupling of C 1 building blocks by a heterometallic Mg–Al complex

Year: 2025

Type: article

Abstract: A heterometallic magnesium–aluminium hydride complex is reported for the selective homologation of C1 building blocks (CO and CNXyl, Xyl = 2,6-dimethylphenyl) to form products containing C2 and C3 chains. CO reacts to form known deltate or ethynediolate motifs with different outcomes depending on the steric demands of the ligand on magnesium. In contrast, CNXyl reacts through a combination of carbon–carbon bond formation and hydride migration to form a novel metalated ethene diamidolate ligand [RN1C1=C2(H)N2R]3–. To our knowledge, this is the first example of such reactivity. DFT calculations support a mechanism in which carbon–carbon bonding is rate-limiting and occurs by the nucleophilic attack of a dimetallated imine intermediate on a coordinated isocyanide group followed by carbon–hydrogen bond formation through hydride migration from Al to C.

Source: Dalton Transactions

DOI: 10.1039/d5dt01351h

Authors: Wenbang Yang, Andrew J. P. White, Mark R. Crimmin

Institution: Imperial College London

Language: English

Topic: Organometallic Complex Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Funder: Engineering and Physical Sciences Research Council

Award: Growing Carbon Chains on Organometallic Networks