An Intermediate Cobalt(IV) Nitrido Complex and its N-Migratory Insertion Product.
Low-temperature photolysis experiments (T = 10 K) on the tripodal azido complex [(BIMPN)Co(N)] ( l) were monitored by EPR spectroscopy and support the formation of an exceedingly reactive, high-valent Co nitrido species [(BIMPN)Co (N)] (2). Density functional theory calculations suggest a low-spin d...
| Publicado en: | Journal of the American Chemical Society Vol. 136; no. 42; pp. 15072 - 15079 |
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| Autores principales: | , , , , , , , |
| Formato: | Artículo |
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American Chemical Society
10/22/2014
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=99414730&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 99414730 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 10/22/2014 vid: 136 iid: 42 pid: 997 pub: American Chemical Society artinfo: ui: 99414730 10.1021/ja508144j ppf: 15072 ppct: 7 formats: tig: atl: An Intermediate Cobalt(IV) Nitrido Complex and its N-Migratory Insertion Product. aug: au: Zolnhofer, Eva M. Käβ, Martina Khusniyarov, Marat M. Heinemann, Frank W. Maron, Laurent van Gaste, Maurice Bill, Eckhard Meyer, Karsten affil: Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander University Erlangen - Niirnberg (FAU), Egerlandstr. 1, 91058 Erlangen, Germany Universite de Toulouse et CNRS, NSA, UPS, CNRS, UMR 5215 LPCNO, 135 avenue de Rangueil, 31077 Toulouse, France Max Planck Institute for Chemical Energy Conversion, Stiftstrafie 34-36, 45470 Miilheim, Germany su: Photolysis (Chemistry) Azido group Electron paramagnetic resonance spectroscopy Density functional theory Nitrides sug: subj: Photolysis (Chemistry) Azido group Electron paramagnetic resonance spectroscopy Density functional theory Nitrides ab: Low-temperature photolysis experiments (T = 10 K) on the tripodal azido complex [(BIMPN)Co(N)] ( l) were monitored by EPR spectroscopy and support the formation of an exceedingly reactive, high-valent Co nitrido species [(BIMPN)Co (N)] (2). Density functional theory calculations suggest a low-spin d, S = 1/2, electronic configuration of the central cobalt ion in 2 and, thus, are in line with the formulation of complex 2 as a genuine, low-spin Co(lV) nitride species. Although the reactivity of this species precludes handling above 50 K or isolation in the solid state, the N-migratory insertion product [(NH-BIMPN)Co](BPh) (3) is isolable and was reproducibly synthesized as well as fully characterized, including CHN elemental analysis, paramagnetic H NMR, IR, UV-vis, and EPR spectroscopy as well as SQUID magnetization and single-crystal X-ray crystallography studies. A computational analysis of the reaction pathway 2 → 3 indicates that the reaction readily occurs via N-migratory insertion into the Co-C bond (activation barrier of 2.2 kcal mol). In addition to the unusual reactivity of the nitride 2, the resulting divalent cobalt complex 3 is a rare example of a trigonal pyramidal complex with four different donor ligands of a tetradentate chelate—an N-heterocyclic carbene, a phenolate, an imine, and an amine—binding to a high-spin Co (II) ion. This renders complex 3 chiral-at-metal. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2014 holdings: @attributes: islocal: N |
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