CONFORMATIONAL INFLUENCE ON DEPROTONATION OF BIS(METHOXYCARBIMIDO)AMINE LIGAND

摘要

Using MP2 treatment,the optimal geometries and corresponding electronic structures of iHN=C(OCH_3)-N-C(OCH_3)=NH]-(mid~-),HN=C(OCH3)-NH-C(OCH_3)=NH(Hmici),[Cu(mici)]_2 and [Cu(Hmici)_2]~(2+)were investigated.In agreement with experimental data,the preferred conformation of our systems depends on the ligand:mici~-prefers the methoxy groups oriented to the central N atom whereas Hmici prefers the opposite orientations.The shielding by the methoxy groups is the main reason for the preferred site of deprotonation.The deprotonation of the [Cu(Hmici)_2]~(2+)complex is more probable than that of the free Hmici ligand.Due to preferred conformation of this complex,the deprotonation proceeds by cleavage of the central N-H bond.