Reversible C-C bond formation in group 4 metal complexes: nitrile extrusion via β-aryl elimination.

ABSTRACT: Pyridylamides of zirconium and hafnium with [C,N,N]-ligands reversibly insert nitriles into M-C_Ar bonds leading to an observable equilibrium between the starting [C,N,N]-complexes and newly formed [N,N,N]-complexes with a ketimide moiety in a 7-membered metallacycle. The discovered reversible insertion of nitriles into M-C_Ar bonds represents an unprecedented example of β-aryl elimination from a ketimide ligand in early transition metal complexes. Experimental and computational studies suggest thermodynamic and electronic reasons for this reactivity. Weak orbital overlap between the ketimide nitrogen and the metal, and an unfavorable 7-membered metallacycle destabilize the product of insertion into the M-C_Ar bond, while the pyridylamide moiety acts as a dire

SUBMITTER: Kulyabin PS 

PROVIDER: S-EPMC11388100 | biostudies-literature | 2024 Aug

REPOSITORIES: biostudies-literature