Two benzoxazoles derivative ligands were synthesized from the condensation of 3,5-di-tert-butyl-o-benzoquinone (DTBBQ)with ethanolamine or 1,3-diamino-2-hydroxypropane in methanol. Condensation of DTBBQ with ethanolamine gives the expected 5,7-di-tert-butyl-2-methylenhydroxylbenzoxazole (HL1)while with 1,3-diamino-2-hydroxypropane it gives (2-hydroxyethyl-2-{2,4- bis(1,1-dimethylethyl)-1-phenol-6 amino}-2{5,7-di-tert-butyl-benzoxazole}) (H ₂L2)with only one benzoxazole ring instead of the symmetric bis-benzoxazole derivative. The structure of HL1 and H ₂L2 were confirmed by NMR-spectroscopy and X-ray diffraction on a single crystal for HL1. The reaction of HL1 with CuCl ₂ gives a mononuclear [Cu ^II(HL1) ₂Cl ₂] (1)complex for which the crystal structure shows that HL1 is preserved. In contrast, upon reaction with nickel( ^II), cobalt( ^II), and manganese( ^II)H ₂L2 is further oxidized and transformed in new ligands HL3 in mononuclear complexes [M ^II(L3) ₂] (M = N ^III (2); M = Co ^II (3))and H ₂L4 in tetranuclear complex [Mn ^II 4(HL4) ₄Cl ₄] (4)as found from the crystal structures of complexes 2-4. Electrochemical studies for complexes 2 and 3 evidence complicated redox properties. [Mn ^II 4(HL4) ₄Cl ₄] (4)has a cubane-like structure with a "4 + 2" fashion The magnetic susceptibility of 4 is well fitted considering one Mn-Mn interaction Ja(Mn ^II-Mn ^II)= -0.50(1)cm-1 with g = 2.00(7).