Synthesis and Aerobic Oxidation of Perfluoroalkyl d10 Metal Complexes Supported by 2,7‐Dimethyl‐1,8‐Naphthyridine

Abstract

AbstractThe coordination chemistry of 2,7‐dimethyl‐1,8‐naphthyridine has been explored with perfluoroalkyl d10 metals, CuI, ZnII, and AgI. This ligand was shown to form dicoordinate CuI and AgI mono‐perfluoroalkyl complexes where naphthyridine coordinates with only one N‐donor, while bidentate coordination with both N‐atoms was observed in Zn bis(perfluoroalkyl) complexes forming a strained four‐membered chelate ring. Copper complexes undergo facile oxidation in the presence of air or excess O2 to give tetracoordinate CuII complexes coordinated to perfluorocarboxylates formed by oxygenation of the metal‐adjacent α‐CF2 position of the corresponding perfluoroalkyl ligands. Another type of product formed by the oxidation of perfluoroethylcopper(I) complexes in the presence of substoichiometric O2 are binuclear CuI⋅⋅⋅CuI complexes with two perfluorocarboxylate ligands. In the presence of an external substrate, alkene, O‐atom transfer was observed to give oxygenated products, resembling the recently reported O‐transfer reactivity of naphthyridine‐supported Ni long‐chain perfluoroalkyl complexes.