Electron Paramagnetic Resonance Study of Copper(II)-tetrammine Nitrate in Solution

The electron paramagnetic resonance of copper (II)-tetram m ine nitrate in solution of methanol and water has been investigated. The data obtained from the spectra at room tem perature and 97 °K together with the optical transition energies determined from single crystal polarized absorption spectra at 77 °K by other authors were used to calculate the LCAO-MO bonding parameters. The bonding orbital of the ammonia molecule cannot be described by the concept of sp2 hybridization which was exclusively used in the theory. Therefore a calculation of the overlap integral S(n) for o bonding and of the superhyperfine splitting was carried out in terms of an arbitrary hybridization param eter n. For ammonia, n was taken from the Duncan-Pople hybrid wave function for the lone pair orbital. The o bonding and the out-of-plane ji bonding appear to have a moderate degree of covalency (« = <5 = 0.91; a ’= 0.49). The covalent in-plane n bonding is somewhat stronger (/? = 0.87) but is by no means so strongly covalent as is observed in compounds with ligands which do not exclusively coordinate through the lone pair electrons. At low temperature nine ligand nuclear superhyperfine structure lines corresponding to the interaction of four magnetically equivalent nitrogen nuclei have been observed. The value of <x' derived from the superhyperfine splitting is in excellent agreement with that obtained from the copper nucleus hyperfine structure.