The Molecular and Electronic Structure of the Electron Transfer Series [Fe2(NO)2(S2C2R2)3]z (z = 0

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• 作者：Prasanta Ghosh ; Eckhard Bill ; Thomas Weyherm&uuml ; ller ; Karl Wieghardt
• 刊名：Inorganic Chemistry
• 出版年：2007
• 出版时间：April 2, 2007
• 年：2007
• 卷：46
• 期：7
• 页码：2612 - 2618
• 全文大小：254K
• 年卷期：v.46,no.7(April 2, 2007)
• ISSN：1520-510X

文摘

Three dinuclear (nitrosyl)iron complexes containing three 1,2-di(phenyl)ethylene-1,2-dithiolate ligands have beenprepared ([Fe₂(NO)₂(S₂C₂R₂)₃]⁰ (R = phenyl, 1a; p-tolyl, 2a; (4-tert-butyl)phenyl, 3a)). Each of these compoundsrepresents the first member of a three-membered electron-transfer series: [Fe₂(NO)₂(S₂C₂R₂)₃]^z (z = 0, -1,, -2).The salt [Co(Cp)₂][Fe₂(NO)₂(L³)₃] has also been isolated. The molecular structures of 2a and 3a have been determinedby X-ray crystallography. Both neutral complexes contain two nearly linear FeNO units, one of which is S,S'-coordinated to two dithiolene ligands yielding a square-based pyramidal Fe(NO)S₄ polyhedron; the second FeNOmoiety forms two (₂-S)-bridges to the first unit and is S,S'-coordinated to a third dithiolate radical yielding also asquare-based pyramidal Fe(NO)S₄ polyhedron. The electronic structures of the neutral, monoanionic, and dianionicspecies have been elucidated spectroscopically (UV-vis, IR, EPR, Mössbauer): [{Fe^II(NO⁺)}(L){Fe^II(O)}(L)₂]⁰(S = 0); [{Fe^II(O)}(L){Fe^II(O)}(L)₂]^1- (S = ¹/₂); and [{Fe^II(O)}(L){Fe^II(O)}(L)₂]^2- (S = 0), where (L)^2-represents the corresponding closed-shell dithiolate dianion and (L)^- is its monoanionic radical.