Conformational control for selective CO2-to-isocyanate conversion in a series of dizinc macrocycle complexes
Year: 2026
Type: preprint
Abstract: Understanding how ligand architecture and conformational flexibility govern reactivity and selectivity in dinuclear metal complexes is essential for the rational design of catalysts. Macrocyclic ligands provide a unique platform to control metalmetal distance as well as the geometry of reactive intermediates; however the relative importance of these factors remains unclear. Herein, we report a series of dinuclear zinc complexes supported by bis(imino)diphenylamido macrocyclic ligands with tunable ring sizes, which exhibit divergent selectivity in CO 2 -to-isocyanate transformations. Varying the linker length between the binding pockets dictates the conformation of key siloxide intermediates, and thus their ability to react further with CO 2 , leading to either isocyanate or silyl ether products. These results establish liganddriven conformational control as a key design principle governing reactivity in dinuclear metal complexes, beyond simple metalmetal distance considerations.
Source: ChemRxiv
Language: English
Subfield: Process Chemistry and Technology
Field: Chemical Engineering
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7214572746