An ab initio molecular orbital study comparing the bonding of the NH3 and the H2O in the monoammines and the monohydrates of main group and transition metal ions

It is common knowledge that some metal ions prefer to bond to nitrogen atoms, others prefer oxygen and others select sulfur, although the mechanistic origin of this behaviour is not well understood. To provide quantitative data that can illuminate this characteristic difference, we have been performing ab initio molecular orbital calculations on complexes of a wide variety of main group and transition metal ions with simple ligands. In this paper we concentrate on metal ion complexes of NH₃ and compare them with the corresponding complexes with H₂O (Trachtman et al., 1998, Inorg. Chem., 37, 4221). The results reported here show that for each metal ion the bonding to ammonia in monoammines is intrinsically stronger than that to water in monohydrates, but that the enthalpy of formation of the amine complexes has a greater sensitivity to the nature of the metal ion. For both mono- and divalent transition metal cations the ligand-field stabilization energy (LFSE) in the monoammine complexes is larger than that in the monohydrates, although the larger enthalpies of formation, ΔH ⁰ ₂₉₈, for the monoammines are due only in part to the larger LFSE values. The formation of both monoammines and monohydrates is accompanied by a transfer of charge from the ligand hydrogen atoms to the metal ion so that there is relatively little change in the net charge on the oxygen or nitrogen atoms. Hence the increased acidity of the ligand in the metal ion complex is not the result of net electron depletion of the atom that is directly bonded to the metal ion, but rather reflects weakening of the bond of that ligand atom to its proton (O-H or N-H). This characteristic is used by many enzymes to promote catalytic activity.