Novel N2O2 tetradentate ligands, H-3BPD and H-2BPD were synthesized. Hydrochloric acid salts of Br-3BPD, Cl-3BPD, Br-2BPD and Cl-2BPD having Br and Cl substituents at the para position of the phenol hydroxyl group, were synthesized. The ligands were characterized by C. H. N atomic analysis, 1H NMR, 13C NMR, UV-visible, and mass spectra. The proton dissociation constants (logKn H) of the phenol hydroxyl group and secondary amine of the synthesized N2O2 ligands were shown by four step wise values. The orders of the calculated overall proton dissociation constants (logβp) were Br-3BPD < Cl-3BPD < H-3BPD in case of 3BPD and Br-2BPD < Cl-2BPD < H-2BPD in case of 2BPD respectively. The order agreed well with that of para Hammett substituent constants(δp). The stability constants(logKML) of the complexes between the synthesized ligands and transition metal(II) ions agreed with the order of logβp of the ligands. The order of the logKML value of the each transition metal (II) ion was Co(Ⅱ) < Ni(Ⅱ) < Cu(Ⅱ) > Zn(Ⅱ) > Cd(Ⅱ) > Pb(Ⅱ), which agreed well with that of Iriving-Williams series.

Hydrochloric acid salt of a new N2O3 pentadentate ligand, N,N'-Bis(2-Hydroxybenzyl)-1,3-diamino-2-propanol(H-BHDP․2HCl) was synthesized. Br-BHDP․2HCl, Cl-BHDP․2HCl, CH3-BHDP․2HCl and CH3O- BHDP․2HCl having Br, Cl, CH3 and CH3O substituents at 5-position of the phenol group of H-BHDP․2HCl were also synthesized. The potentiometry study in aqueous solution revealed that the proton dissociations of the synthesized ligands occurred in four steps and their order of the calculated overall proton dissociation constants(logβp) was Br-BHDP〈 Cl-BHDP〈 H-BHDP〈 CH3O-BHDP〈 CH3-BHDP. The order showed a similar trend to that of Hammett substituent constants(δp). The order of the stability constants(logKML) was Co(Ⅱ)〈 Ni(Ⅱ)〈 Cu(Ⅱ)〈 Zn(Ⅱ)〈 Cd(Ⅱ)〈 Pb(Ⅱ). The order in their stability constants (logKML) of each transition metal complex agreed with that of the overall proton dissociation constants (logβp).