Nickel Complexes of o-Amidochalcogenophenolate(2−)/o-Iminochalcogenobenzosemiquinonate(1−) π-Radical: Synthesis, Structures, Electron Spin Resonance, and X-ray Absorption Spectroscopic Evidence
學年 91
學期 2
出版（發表）日期 2003-06-01
作品名稱 Nickel Complexes of o-Amidochalcogenophenolate(2−)/o-Iminochalcogenobenzosemiquinonate(1−) π-Radical: Synthesis, Structures, Electron Spin Resonance, and X-ray Absorption Spectroscopic Evidence
作品名稱（其他語言）
著者 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
單位 淡江大學化學學系
出版者 Washington, DC: American Chemical Society
著錄名稱、卷期、頁數 Inorganic Chemistry 42(12), pp.3925–3933
摘要 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.
關鍵字
語言 en
ISSN 0020-1669 1520-510X
期刊性質 國外
收錄於
產學合作
通訊作者
審稿制度 是
國別 USA
公開徵稿
出版型式 紙本 電子版
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