Unsymmetrical amine tris(phenolate) ligands have been prepared and complexed to Zr(iv). In the solid-state dimeric species are observed, which persist in solution. The complexes show interesting coordination chemistry and the nature of which is discussed. These complexes are analogues of a highly stereoselective C3-symmetric Zr(iv) amine tris(phenolate) alkoxide and have been prepared, characterised and trialled for the ring-opening of rac-lactide providing insight into the effect of symmetry and ligand steric bulk on selectivity. The polymerisations have been investigated in solution and under the industrially preferred melt conditions (130 °C). The rate law for the ROP has been determined-with Zr2(1)2(O iPr)2, a pseudo first order dependency was seen, however for Zr2(2)2(OiPr)2 this changed to a half order dependency in initiator.