Self-assembly in the metallation of bis(aminoaryl) ethers

Abstract

The dilithiation of 2,2′-bis(2-methoxyethylamino)diphenyl ether (4) and 2,2′-bis(N,N-dimethylethylenediamino)diphenyl ether (7) in the absence of any Lewis base donor resulted in the formation of dimeric complexes 8 and 9, respectively, containing the unprecedented Li4O2N4 "adamantanoid" metal core as a consequence of the self-recognition and self-assembly involving the two metallated subunits. In contrast, on monometallation using particular conditions, e.g. sodium hydride in the presence of Lewis base donor, the same ligands undergo a Smiles-type rearrangement, providing the first example of such a reaction involving an amine and a deactivated aromatic system. The conditions needed to promote this rearrangement have been investigated. © 1994.