Reactions of the η5-2,5-dimethylthiophene complex Cp ∗Ir(η 5-2,5-Me 2T) 2+ with nucleophiles (Ph −, Me −, −CH(CO 2Me) 2 and OH −) 1

Abstract

Cp ∗Ir(η 5-2,5-Me 2T) 2+ ( 1), where Cp ∗ = η 5- C 5 Me 5 and 2,5- Me 2 T = 2,5- dimethylthiophene , reacts with PhLi to give Cp ∗Ir(2,5-Me 2T·2Ph) and the acylthiolate Cp ∗Ir(η 4-SC 3H 2MeC(=O)Me) ( 3) which incorporates oxygen from the tetrahydrofuran solvent and whose structure was established crystallographically. The analogous reaction of 1 with MeLi gives Cp ∗Ir(2,5-Me 2T · 2Me). Complex 1 reacts with −CH(CO 2Me) 2 to give Cp ∗Ir(η 4-2,5-Me 2T · C(CO 2Me) 2) ( 6), which contains an opened-ring thiolate ligand. With OH −, 1 gives both 3 and Cp ∗Ir(η 4-2,5-Me 2T · O) ( 7), which incorporates a thiophene S-oxide ligand. These reactions are discussed in the context of related reactions of η 5-thiophene complexes in the literature.