title: Synthesis, structure, and magnetism of an f element nitrosyl complex, (C5Me4H)3UNO.
abstract: (C(5)Me(4)H)(3)U, 1, reacts with 1 equiv of NO to form the first f element nitrosyl complex (C(5)Me(4)H)(3)UNO, 2. X-ray crystallography revealed a 180° U-N-O bond angle, typical for (NO)(1+) complexes. However, 2 has a 1.231(5) Å N═O distance in the range for (NO)(1-) complexes and a short 2.013(4) Å U-N bond like the U═N bond of uranium imido complexes. Structural, spectroscopic, and magnetic data as well as DFT calculations suggest that reduction of NO by U(3+) has occurred to form a U(4+) complex of (NO)(1-) that has π interactions between uranium 5f orbitals and NO π* orbitals. These bonding interactions account for the linear geometry and short U-N bond. The complex displays temperature-independent paramagnetism with a magnetic moment of 1.36 μ(B) at room temperature. Complex 2 reacts with Al(2)Me(6) to form the adduct (C(5)Me(4)H)(3)UNO(AlMe(3)), 3.
authors.affiliation: Department of Chemistry, University of California, Irvine, California 92627-2025, USA.
authors.forename: Nathan A
authors.initials: NA
authors.lastname: Siladke
authors.forename: Katie R
authors.initials: KR
authors.lastname: Meihaus
authors.forename: Joseph W
authors.initials: JW
authors.lastname: Ziller
authors.forename: Ming
authors.initials: M
authors.lastname: Fang
authors.forename: Filipp
authors.initials: F
authors.lastname: Furche
authors.forename: Jeffrey R
authors.initials: JR
authors.lastname: Long
authors.forename: William J
authors.initials: WJ
authors.lastname: Evans