Late‐stage Ligand Modification After Coordination Strengthens Stereoselectively Self‐Assembled Hemiaminal Ether Complexes

Fragile hemiaminal ether linkages present in the backbone of koneramines (LROR’), tridentate ligands, bound to copper(II) in stereoselectively self‐assembled syn‐[Cu(LROR’)X2] complexes were transformed into sturdy methylene linkages to make corresponding rac‐[Cu(LRH)Cl2] complexes by late‐stage ligand modification after coordination with the retention of coordination sphere. The generality of stereoselective self‐assembly of koneramine complexes is shown by utilising a number of metal ions, anions, amines, alcohols and thiols with complete characterisations. Fragile hemiaminal ether linkages present in the backbone of koneramine ligands bound to copper(II) in stereoselectively self‐assembled complexes were transformed into sturdy methylene linkages by late‐stage ligand modification after coordination with the retention of coordination sphere.