Thermal Studies of Metal-quinone Complexes Role of Aqua Coligations with Copper(II) in Coordination of 2-hydroxy-1,4-naphthoquinone

Copper(II) complexes of lawsone (2-hydroxy-1,4-naphthaquinone, Lw) with variety of aqua ligation viz. Cu-1, Cu(Lw)₂(H₂O)]₂; Cu-2, Cu(Lw)₂(H₂O)₂] and Cu-3, Cu(Lw)₂(H₂O)₂]₂ have been synthesized. The role of water as counter ligand on coordination propensity of redox active lawsone in naphthoquinone/naphthosemiquinone (NQ/NSQ) forms is quantified by studies of pyrolytic reactions, using non-isothermal TG and DTA techniques, coupled with IR studies. Mixed (NQ) (NSQ) ligation in Cu-1 and Cu-3 required energy of activation, E_a ∼67 kJ mol⁻¹ of (NQ) and ∼41 kJ mol⁻¹ of (NSQ). Comparable energies of aqua ligand (∼43 kJ mol⁻¹) with NSQ ligand in Cu-1 and Cu-3, dictate charge distributions in lawsone coordinations. A large difference between E_a of aqua and p-NQ ligand indicates coordination of lawsone in its fully oxidised quinone form in Cu-2. From thermoanalytical studies schematic oxidative decomposition mechanisms are proposed for Cu-1 and Cu-3. From pyrolytic reactions enthalpies are estimated by DTA technique. This revised version was published online in August 2006 with corrections to the Cover Date.