title: Distorted tetrahedral nickel-nitrosyl complexes: spectroscopic characterization and electronic structure.
abstract: The linear nickel-nitrosyl complex [Ni(NO)(L3)] supported by a highly hindered tridentate nitrogen-based ligand, hydrotris(3-tertiary butyl-5-isopropyl-1-pyrazolyl)borate (denoted as L3), was prepared by the reaction of the potassium salt of the ligand with the nickel-nitrosyl precursor [Ni(NO)(Br)(PPh 3 ) 2 ]. The obtained nitrosyl complexes as well as the corresponding chlorido complexes [Ni(NO)(Cl)(PPh 3 ) 2 ] and [Ni(Cl)(L3)] were characterized by X-ray crystallography and different spectroscopic methods including IR/far-IR, UV-Vis, NMR, and multi-edge X-ray absorption spectroscopy at the Ni K-, Ni L-, Cl K-, and P K-edges. For comparative electronic structure analysis we also performed DFT calculations to further elucidate the electronic structure of [Ni(NO)(L3)]. These results provide the nickel oxidation state and the character of the Ni-NO bond. The complex [Ni(NO)(L3)] is best described as [Ni (II) (NO (-) )(L3)], and the spectroscopic results indicate that the phosphane complexes have a similar [Ni (II) (NO (-) )(X)(PPh 3 ) 2 ] ground state.
authors.affiliation: Department of Chemistry, Ibaraki University, Mito, Ibaraki, 310-8512, Japan.
authors.forename: Shoko
authors.initials: S
authors.lastname: Soma
authors.affiliation: Department of Chemistry and Department of Biophysics, University of Michigan, 930 N. University Avenue, Ann Arbor, MI, 48109, USA.|Max Planck Institute for Chemical Energy Conversion, Stiftstraße 34-36, 45470, Mülheim an der Ruhr, Germany.
authors.forename: Casey
authors.initials: C
authors.lastname: Van Stappen
authors.affiliation: MTA-ELTE Chemical Structure & Function "Momentum" Laboratory, Budapest, Hungary.
authors.forename: Mercedesz
authors.initials: M
authors.lastname: Kiss
authors.affiliation: MTA-ELTE Chemical Structure & Function "Momentum" Laboratory, Budapest, Hungary. szilagyi@montana.edu.|Department of Chemistry and Biochemistry, Montana State University, Bozeman, MT, 59717, USA. szilagyi@montana.edu.
authors.forename: Robert K
authors.initials: RK
authors.lastname: Szilagyi
authors.affiliation: Department of Chemistry and Department of Biophysics, University of Michigan, 930 N. University Avenue, Ann Arbor, MI, 48109, USA. lehnertn@umich.edu.
authors.forename: Nicolai
authors.initials: N
authors.lastname: Lehnert
authors.affiliation: Department of Chemistry, Ibaraki University, Mito, Ibaraki, 310-8512, Japan. kiyoshi.fujisawa.sci@vc.ibaraki.ac.jp.
authors.forename: Kiyoshi
authors.initials: K
authors.lastname: Fujisawa
mesh_terms: D018360:Crystallography, X-Ray; D004583:Electrons; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D009589:Nitrogen Oxides / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D011789:Quantum Theory; D013055:Spectrophotometry, Infrared; D013056:Spectrophotometry, Ultraviolet; D056928:X-Ray Absorption Spectroscopy
chemical_list: D009589:Nitrogen Oxides; D009942:Organometallic Compounds; D009532:Nickel
keywords: DFT calculations; Nickel; Nitrosyl; X-ray absorption; X-ray structure