Nickel Complexes of o-Amidochalcogenophenolate(2−)/o-Iminochalcogenobenzosemiquinonate(1−) π-Radical: Synthesis, Structures, Electron Spin Resonance, and X-ray Absorption Spectroscopic Evidence

doi:10.1021/ic034211r

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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

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