Work

Accessing Ta/Cu Architectures via Metal‐Metal Salt Metatheses: Heterobimetallic C−H Bond Activation Affords μ‐Hydrides

Year: 2023

Type: article

Abstract: We employ a metal‐metal salt metathesis strategy to access low‐valent tantalum‐copper heterometallic architectures (Ta−μ2‐H2−Cu and Ta−μ3‐H2−Cu3) that emulate structural elements proposed for surface alloyed nanomaterials. Whereas cluster assembly with carbonylmetalates is well precedented, the use of the corresponding polyarene transition metal anions is underexplored, despite recognition of these highly reactive fragments as storable sources of atomic Mn−. Our application of this strategy provides structurally unique early‐late bimetallic species. These complexes incorporate bridging hydride ligands during their syntheses, the origin of which is elucidated via detailed isotopic labelling studies. Modification of ancillary ligand sterics and electronics alters the mechanism of bimetallic assembly; a trinuclear complex resulting from dinuclear C−H activation is demonstrated as an intermediate en route to formation of the bimetallic. Further validating the promise of this rational, bottom‐up approach, a unique tetranuclear species was synthesized, featuring a Ta centre bearing three Ta−Cu interactions.

Source: Angewandte Chemie

DOI: 10.1002/ange.202311721

Authors: Michela L. Maiola, Joshua A. Buss

Institution: University of Michigan

Language: English

Topic: Organometallic Complex Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $5,250

Funder: National Science Foundation