title: Trigonal bipyramidal iron(III) and manganese(III) oxo, sulfido, and selenido complexes. An electronic-structural overview.
abstract: Using density functional theory calculations, we have carried out a broad survey of trigonal bipyramidal iron(III) and manganese(III) oxo, sulfido, selenido, and hydroxo complexes, with tripodal tetradentate "triureidoamine" supporting ligands. The calculations reproduce the experimentally observed high-spin states of these compounds; a multifunctional analysis suggests that the high-spin nature of these species follows largely from their trigonal bipyramidal geometry. In conjunction with earlier calculations, the present study provides a broad overview of spin density profiles in iron-oxo species in general. Iron-oxo d(pi)-p(pi) interactions invariably result in a substantial spin density on the oxygen, which in turn may be significantly tuned by hydrogen bonding interactions. The oxygen spin densities are smaller in analogous manganese-oxo species, indicating that manganese is less adept at pi-bonding than iron, which parallels earlier findings on porphyrin systems. The Fe(III)-S/Se spin density profiles provide one of the first confirmations in a transition metal context of Schleyer's prediction that the heavier p-block elements are as effective as their second-row congeners in terms of their pi-donating ability.
authors.affiliation: Department of Chemistry, University of Tromsø, Breivika, N-9037 Tromsø, Norway.
authors.forename: Jeanet
authors.initials: J
authors.lastname: Conradie
authors.forename: Espen
authors.initials: E
authors.lastname: Tangen
authors.forename: Abhik
authors.initials: A
authors.lastname: Ghosh
mesh_terms: D005290:Ferric Compounds / Q000737:chemistry*; D006860:Hydrogen Bonding; D017895:Manganese Compounds / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D018036:Selenium Compounds / Q000737:chemistry*; D013457:Sulfur Compounds / Q000737:chemistry*
chemical_list: D005290:Ferric Compounds; D017895:Manganese Compounds; D018036:Selenium Compounds; D013457:Sulfur Compounds; D010100:Oxygen