title: Stability studies of transition-metal linkage isomers using quantum mechanical methods. Groups 11 and 12 transition metals.
abstract: Several hypotheses to elucidate the linkage isomer preference of the thiocyanate (SCN(-)) ion have been offered. For complexes with small coordination numbers (i.e., 1 and 2) and groups 11 (Cu-triad) and 12 (Zn-triad) metals, different levels of theory and a variety of basis sets have been employed to study linkage isomerism. Similar results are obtained for all density functionals tested, pure and hybrid. Overall, good agreement, vis-à-vis experimentally identified linkage isomers, is achieved for ab initio techniques, whereas semiempirical quantum mechanical methods show a bias toward S-ligated isomers. Despite the seeming ease for the a priori prediction of the most stable thiocyanate isomers using acid/base principles, this research highlights the sensitivity of quantitative calculations of transition-metal linkage isomerism to the choice of basis set and electron correlation, particularly with post-Hartree-Fock treatments.
authors.affiliation: Department of Chemistry, University of North Texas, Denton, Texas 76203, USA.
authors.forename: Corneliu
authors.initials: C
authors.lastname: Buda
authors.forename: Abul B
authors.initials: AB
authors.lastname: Kazi
authors.forename: Adriana
authors.initials: A
authors.lastname: Dinescu
authors.forename: Thomas R
authors.initials: TR
authors.lastname: Cundari