English  |  正體中文  |  简体中文  |  Items with full text/Total items : 62570/95226 (66%)
Visitors : 2508588      Online Users : 237
RC Version 7.0 © Powered By DSPACE, MIT. Enhanced by NTU Library & TKU Library IR team.
Scope Tips:
  • please add "double quotation mark" for query phrases to get precise results
  • please goto advance search for comprehansive author search
  • Adv. Search
    HomeLoginUploadHelpAboutAdminister Goto mobile version
    Please use this identifier to cite or link to this item: https://tkuir.lib.tku.edu.tw/dspace/handle/987654321/97586

    Title: Nickel Complexes of o-Amidochalcogenophenolate(2−)/o-Iminochalcogenobenzosemiquinonate(1−) π-Radical: Synthesis, Structures, Electron Spin Resonance, and X-ray Absorption Spectroscopic Evidence
    Authors: Hsieh, Chung-Hung;Hsu, I-Jui;Lee, Chien-Ming;Ke, Shyue-Chu;Wang, Tze-Yuan;Lee, Gene-Hsiang;Wang, Yu;Chen, Jin-Ming;Lee, Jyh-Fu;Liaw, Wen-Feng
    Contributors: 淡江大學化學學系
    Date: 2003-06
    Issue Date: 2014-03-27 15:31:46 (UTC+8)
    Publisher: Washington, DC: American Chemical Society
    Abstract: The preparation of complexes trans-[Ni(−SeC6H4-o-NH−)2]- (1), cis-[Ni(−TeC6H4-o-NH−)2]- (2), trans-[Ni(−SC6H4-o-NH−)2]- (3), and [Ni(−SC6H4-o-S−)2]- (4) by oxidative addition of 2-aminophenyl dichalcogenides to anionic [Ni(CO)(SePh)3]- proves to be a successful approach in this direction. The cis arrangement of the two tellurium atoms in complex 2 is attributed to the intramolecular Te···Te contact interaction (Te···Te contact distance of 3.455 Å). The UV−vis electronic spectra of complexes 1 and 2 exhibit an intense absorption at 936 and 942 nm, respectively, with extinction coefficient ε > 10000 L mol-1 cm-1. The observed small g anisotropy, the principal g values at g1 = 2.036, g2 = 2.062, and g3 = 2.120 for 1 and g1 = 2.021, g2 = 2.119, and g3 = 2.250 for 2, respectively, indicates the ligand radical character accompanied by the contribution of the singly occupied d orbital of Ni(III). The X-ray absorption spectra of all four complexes show LIII peaks at 854.5 and 853.5 eV. This may indicate a variation of contribution of the Ni(II)−Ni(III) valence state. According to the DFT calculation, the unpaired electron of complex 1 and 2 is mainly distributed on the 3dxz orbital of the nickel ion and on the 4pz orbital of selenium (tellurium, 5pz) as well as the 2pz orbital of nitrogen of the ligand. On the basis of X-ray structural data, UV−vis absorption, electron spin resonance, magnetic properties, DFT computation, and X-ray absorption (K- and L-edge) spectroscopy, the monoanionic trans-[Ni(−SeC6H4-o-NH−)2]- and cis-[Ni(−TeC6H4-o-NH−)2]- complexes are appositely described as a resonance hybrid form of Ni(III)−bis(o-amidochalcogenophenolato(2−)) and Ni(II)−(o-amidochalcogenophenolato(2−))−(o-iminochalcogenobenzosemiquinonato(1−) π-radical; i.e., complexes 1 and 2 contain delocalized oxidation levels of the nickel ion and ligands.
    Relation: Inorganic Chemistry 42(12), pp.3925–3933
    DOI: 10.1021/ic034211r
    Appears in Collections:[Graduate Institute & Department of Chemistry] Journal Article

    Files in This Item:

    File Description SizeFormat
    Nickel Complexes of o-Amidochalcogenophenolate(2−) o-Iminochalcogenobenzosemiquinonate(1−) π-Radical Synthesis Structures Electron Spin Resonance and X-ray Absorption Spectroscopic Evidence.pdf205KbAdobe PDF1View/Open

    All items in 機構典藏 are protected by copyright, with all rights reserved.

    DSpace Software Copyright © 2002-2004  MIT &  Hewlett-Packard  /   Enhanced by   NTU Library & TKU Library IR teams. Copyright ©   - Feedback