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Spectroscopic studies of someCuI andCuII complexes derived by tribochemical reactions of some thiosemicarbazide derivatives containingGirard’s P with KI

S.M.A.Al-Ashqar, M.M.Mostafa

The novel starting CuII complex with the general formula,[CuL1Cl2.H2O]Cl. ½EtOH (L1=N-{[(phenylaminomethyl) thioxomethyl] hydrazinocarbonylmethyl} pyridiniumchloride (PTHPC),was synthesized by conventional chemicalmethod. The tribochemical reaction of thisCuII complex,[CuL1Cl2.H2O]Cl. ½EtOH, with KI affords a novel CuI complex with the general formula,[Cu(L1')I]I.7H2O. The ligand (L1') has the same formula as L1 except that the ionizable chloride ion in L1 is substituted by iodide ion in case of L1' during the tribochemical reaction. Also, the CuII complex is reduced to CuI during the tribochemical reaction. The IR spectra of the CuII and CuI complexes suggest that both the ligands (L1, L2') coordinate in a tridentate manner via the carbonyl oxygen (C=O), NH2 and thioketo (C=S) groups. The spectral and magnetic results suggest a distorted-octahedral geometry for the CuII complex prepared by conventional chemicalmethod while a squareplanar structure for the CuI complex synthesized by the tribochemical reaction. The mechanism of the reduction of CuII complex to CuI as well as the change of the color during the tribochemical reaction is discussed.