Multiple bonding involving late transition metals. The case of a silver-oxo complex

Calculations at a variety of theoretical levels were carried out on putativ e silver-oxo species, models of an experimentally proposed complex. Additio nally, statistical analysis of metal-ore bond lengths involving the early a nd middle transition series metals was carried out. This work casts doubt o n the formulation of a reported complex as a diamagnetic, Ag(III)-oxo speci es. Two major points of contention are found. First, a cationic Ag(III)-oxo species is predicted to have a triplet ground state, with the singlet lyin g much higher in energy. Even the tripler would be an unstable species, due to its very low predicted bond energy. Second, the experimentally determin ed "silver-oxo" bond length of 1.59 Angstrom is very short in comparison to values obtained from calculation and estimated from the crystal structures of other metal-ore species.