Transition Metal Promoted Oxidative C–N Fusion Reactions of Aromatic Amines and Their Coordination Chemistry

Abstract

Some unusual examples of metal promoted oxidative dimerization and polymerization, via C–N bond formation, of aromatic mono- as well as di-amines are described. Successful isolation and thorough characterization of the products follow these reactions. Electrochemical and spectral studies of the complexes are reported and compared with related systems. While the heavier transition metal ions like ruthenium(III) and osmium(IV) mediate ortho-dimerization of primary amines, ArNH₂, Fe(III), on the other hand, promotes polymerization. Similar fusion reaction of 1,3-diaminobenzene with the mediator complex, [Ru(acac)₃] (acac=acetyl acetonate), led to the formation of diruthenium complexes.

Keywords:

• metal-mediation
• organic transformation
• metal-diimines
• X-ray structures
• redox