New Members of a Class of Iron−Thiolate−Nitrosyl Compounds: Trinuclear Iron−Thiolate−Nitrosyl Complexes Containing Fe3S6 Core

doi:10.1021/ja065401e

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題名:	New Members of a Class of Iron−Thiolate−Nitrosyl Compounds: Trinuclear Iron−Thiolate−Nitrosyl Complexes Containing Fe3S6 Core
作者:	Hsu, I-Jui;Hsieh, Chung-Hung;Ke, Shyue-Chu;Chiang, Kuo-An;Lee, Jenn-Min;Chen, Jin-Ming;Jang, Ling-Yun;Lee, Gene-Hsiang;Wang, Yu;Liaw, Wen-Feng
貢獻者:	淡江大學化學學系
日期:	2007-02
上傳時間:	2014-03-27 11:34:06 (UTC+8)
出版者:	Washington, DC: American Chemical Society
摘要:	The neutral trinuclear iron−thiolate−nitrosyl, [(ON)Fe(μ-S,S-C6H4)]3 (1), and its oxidation product, [(ON)Fe(μ-S,S-C6H4)]3[PF6] (2), were synthesized and characterized by IR, X-ray diffraction, X-ray absorption, electron paramagnetic resonance (EPR), and magnetic measurement. The five-coordinated, square pyramidal geometry around each iron atom in complex 1 remains intact when complex 1 is oxidized to yield complex 2. Magnetic measurements and EPR results show that there is only one unpaired electron in complex 1 (Stotal = 1/2) and no unpaired electron (Stotal = 0) in 2. The detailed geometric comparisons between complexes 1 and 2 provide understanding of the role that the unpaired electron plays in the chemical bonding of this trinuclear complex. Significant shortening of the Fe−Fe, Fe−N, and Fe−S distances around Fe(1) is observed when complex 1 is oxidized to 2. This result implicates that the removal of the unpaired electron does induce the strengthening of the Fe−Fe, Fe−N, and Fe−S bonds in the Fe(1) fragment. A significant shift of the νNO stretching frequency from 1751 cm-1 (1) to 1821, 1857 cm-1 (2) (KBr) also indicates the strengthening of the N−O bonds in complex 2. The EPR, X-ray absorption, magnetic measurements, and molecular orbital calculations lead to the conclusion that the unpaired electron in complex 1 is mainly allocated in the Fe(1) fragment and is best described as {Fe(1)NO}7, so that the unpaired electron is delocalized between Fe and NO via d−π* orbital interaction; some contributions from [Fe(2)NO] and [Fe(3)NO] as well as the thiolates associated with Fe (1) are also realized. According to MO calculations, the spin density of complex 1 is predominately located at the Fe atoms with 0.60, −0.15, and 0.25 at Fe(1), Fe(2), and Fe(3), respectively.
關聯:	Journal of the American Chemical Society 129(5), pp.1151-1159
DOI:	10.1021/ja065401e
顯示於類別:	[化學學系暨研究所] 期刊論文

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