RESUMO
Treatment of [UO(2)(Ar(2)nacnac)Cl](2) with 4 equiv. of Li(C(4)H(5)N(2)) results in the formation of a rare uranyl organometallic complex [Li(MeIm)][UO(µ-O)(Ar(2)nacnac)(µ-C,N-C(4)H(5)N(2))(2)] (2), in moderate yield. Reaction of 2 with 1 equiv. of MCl(2) (M = Fe, Co) yields the bimetallic complexes [MCl(MeIm)][UO(2)(Ar(2)nacnac)(µ-N,C-C(4)H(5)N(2))(2)] (M = Fe, 3; M = Co, 4).
Assuntos
Imidazóis/química , Compostos Organometálicos/química , Compostos Organometálicos/síntese química , Compostos de Urânio/química , Lítio/química , Modelos Moleculares , Estrutura MolecularRESUMO
Addition of 2 equiv of AgOTf to [UO(2)(Ar(2)nacnac)Cl](2) (Ar(2)nacnac = {(2,6-Pr(i)(2)C(6)H(3))NC(Me)}(2)CH) in the presence of excess pyridine, followed by addition of Cp(2)Co, generates the uranyl(V) complex UO(2)(Ar(2)nacnac)(py)(2) (2), in moderate yield. Complex 2 has proven to be an excellent precursor for the synthesis of other U(V) complexes. Thus, addition of 2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), TMEDA, or 1-methylimidazole (MeIm) to 2 provides UO(2)(Ar(2)nacnac)(bipy) (3), UO(2)(Ar(2)nacnac)(phen) (4), UO(2)(Ar(2)nacnac)(TMEDA) (5), and UO(2)(Ar(2)nacnac)(MeIm)(2) (6), respectively. Complexes 2-6 have been fully characterized and their structures confirmed by X-ray crystallography. Attempts to form the analogous hexavalent uranyl complexes of bipy, phen, and TMEDA have not been successful. However, reaction of [UO(2)(Ar(2)nacnac)Cl](2) with AgOTf and 2 equiv of MeIm leads to the isolation of [UO(2)(Ar(2)nacnac)(MeIm)(2)][OTf] (7), which has been fully characterized. Attempts to ligate sulfur donor ligands to either the UO(2)(Ar(2)nacnac) or the [UO(2)(Ar(2)nacnac)](+) fragments were unsuccessful.
