title: Multiple Bonding Involving Late Transition Metals. The Case of a Silver-Oxo Complex.
abstract: Calculations at a variety of theoretical levels were carried out on putative silver-oxo species, models of an experimentally proposed complex. Additionally, statistical analysis of metal-oxo bond lengths involving the early and middle transition series metals was carried out. This work casts doubt on the formulation of a reported complex as a diamagnetic, Ag(III)-oxo species. 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 lying much higher in energy. Even the triplet would be an unstable species, due to its very low predicted bond energy. Second, the experimentally determined "silver-oxo" bond length of 1.59 Å is very short in comparison to values obtained from calculation and estimated from the crystal structures of other metal-oxo species.
authors.affiliation: Department of Chemistry, Computational Research on Materials Institute (CROMIUM), The University of Memphis, Memphis, Tennessee 38152-6060, and School of Chemistry, University of Bristol, Bristol BS8 1TS, U.K.
authors.forename: Thomas R.
authors.initials: TR
authors.lastname: Cundari
authors.forename: Jeremy N.
authors.initials: JN
authors.lastname: Harvey
authors.forename: Thomas R.
authors.initials: TR
authors.lastname: Klinckman
authors.forename: Wentao
authors.initials: W
authors.lastname: Fu