title: Manganese nitride complexes in oxidation states III, IV, and V: synthesis and electronic structure.
abstract: The synthesis and characterization of a series of manganese nitrides in a tripodal chelating tris(carbene) ligand framework is described. Photolysis of [(TIMEN(xyl))Mn(N(3))](+) (where TIMEN(xyl) = tris[2-(3-xylylimidazol-2-ylidene)ethyl]amine) yields the isolable molecular Mn(IV) nitride, [(TIMEN(xyl))Mn(N)](+). Spectroscopic and DFT studies indicate that this Mn(IV) d(3) complex has a doublet electronic ground state. The metal-centered one-electron oxidation of this Mn(IV) species results in formation of the pentavalent Mn(V) nitride, [(TIMEN(xyl))Mn(N)](2+). Unlike previously reported, tetragonal Mn(V) nitrides with a d(2), nonmagnetic S = 0 ground state, this trigonal bipyramidal complex has a triplet ground state S = 1. One-electron reduction of [(TIMEN(xyl))Mn(N)](+) produces the neutral, nonmagnetic trivalent [(TIMEN(xyl))Mn(N)] species with a d(4) low-spin, S = 0, ground state.
authors.affiliation: Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander University of Erlangen-Nuremberg, Egerlandstrasse 1, Erlangen, Germany.
authors.forename: Henning
authors.initials: H
authors.lastname: Kropp
authors.forename: Amanda E
authors.initials: AE
authors.lastname: King
authors.forename: Marat M
authors.initials: MM
authors.lastname: Khusniyarov
authors.forename: Frank W
authors.initials: FW
authors.lastname: Heinemann
authors.forename: Kyle M
authors.initials: KM
authors.lastname: Lancaster
authors.forename: Serena
authors.initials: S
authors.lastname: DeBeer
authors.forename: Eckhard
authors.initials: E
authors.lastname: Bill
authors.forename: Karsten
authors.initials: K
authors.lastname: Meyer
mesh_terms: D004583:Electrons; D008345:Manganese / Q000737:chemistry*; D008958:Models, Molecular; D010084:Oxidation-Reduction
chemical_list: D008345:Manganese