Radical anionic versus neutral 2,2′-bipyridyl coordination in uranium complexes supported by amide and ketimide ligands

Abstract

The synthesis and characterization of (bipy)₂U(N[t-Bu]Ar)₂ (1-(bipy)₂, bipy = 2,2′-bipyridyl, Ar = 3,5-C₆H₃Me₂), (bipy)U(N[¹Ad]Ar)₃ (2-bipy), (bipy)₂U(NC[t-Bu]Mes)₃ (3-(bipy)₂, Mes = 2,4,6-C₆H₂Me₃), and IU(bipy)(NC[t-Bu]Mes)₃ (3-I-bipy) are reported. X-ray crystallography studies indicate that bipy coordinates as a radical anion in 1-(bipy)₂ and 2-bipy, and as a neutral ligand in 3-I-bipy. In 3-(bipy)₂, one of the bipy ligands is best viewed as a radical anion, the other as a neutral ligand. The electronic structure assignments are supported by NMR spectroscopy studies of exchange experiments with 4,4′-dimethyl-2,2′-bipyridyl and also by optical spectroscopy. In all complexes, uranium was assigned a +4 formal oxidation state.