SELF-ASSEMBLY IN THE METALATION OF BIS(AMINOARYL) ETHERS

The dilithiation of 2,2'-bis(2-methoxyethylamino)diphenyl ether (4) an d 2,2'-bis(N,N-dimethylethylenediamino)diphenyl ether (7) in the absen ce of any Lewis base donor resulted in the formation of dimeric comple xes 8 and 9, respectively, containing the unprecedented Li4O2N4 ''adam antanoid'' metal core as a consequence of the self-recognition and sel f-assembly involving the two metallated subunits. In contrast, on mono metallation using particular conditions, e.g. sodium hydride in the pr esence of Lewis base donor, the same ligands undergo a Smiles-type rea rrangement, providing the first example of such a reaction involving a n amine and a deactivated aromatic system. The conditions needed to pr omote this rearrangement have been investigated.