Structural and Electronic Responses to the Three Redox Levels of Fe(NO)​N2S2-​Fe(NO)​(2)
學年 107
學期 1
出版（發表）日期 2018-09-14
作品名稱 Structural and Electronic Responses to the Three Redox Levels of Fe(NO)​N2S2-​Fe(NO)​(2)
作品名稱（其他語言）
著者 Ghosh, Pokhraj; Ding, Shengda; Quiroz, Manuel; Bhuvanesh, Nattamai; Hsieh, Chung-Hung; Palacios, Philip M.; Pierce, Brad S.; Darensbourg, Marcetta Y.; Hall, Michael B.
單位
出版者
著錄名稱、卷期、頁數 Chemistry - A European Journal 24(60), p.16003-16008
摘要 The nitrosylated diiron complexes, Fe2(NO)3, of this study are interpreted as a mono‐nitrosyl Fe(NO) unit, MNIU, within an N2S2 ligand field that serves as a metallodithiolate ligand to a dinitrosyl iron unit, DNIU. The cationic Fe(NO)N2S2⋅Fe(NO)2+ complex, 1+, of Enemark–Feltham electronic notation {Fe(NO)}7‐{Fe(NO)2}9, is readily obtained via myriad synthetic routes, and shown to be spin coupled and diamagnetic. Its singly and doubly reduced forms, {Fe(NO)}7‐{Fe(NO)2}10, 10, and {Fe(NO)}8‐{Fe(NO)2}10, 1−, were isolated and characterized. While structural parameters of the DNIU are largely unaffected by redox levels, the MNIU readily responds; the neutral, S=urn:x-wiley:09476539:media:chem201804168:chem201804168-math-0001 , complex, 10, finds the extra electron density added into the DNIU affects the adjacent MNIU as seen by the decrease its Fe‐N‐O angle (from 171° to 149°). In contrast, addition of the second electron, now into the MNIU, returns the Fe‐N‐O angle to 171° in 1−. Compensating shifts in FeMNIU distances from the N2S2 plane (from 0.518 to 0.551 to 0.851 Å) contribute to the stability of the bimetallic complex. These features are addressed by computational studies which indicate that the MNIU in 1− is a triplet‐state {Fe(NO)}8 with strong spin polarization in the more linear FeNO unit. Magnetic susceptibility and parallel mode EPR results are consistent with the triplet state assignment.
關鍵字 diiron;electron buffer;EPR;metallodithiolate ligand;nitric oxide;redox levels
語言 en
ISSN
期刊性質 國外
收錄於 SCI
產學合作
通訊作者
審稿制度 否
國別 USA
公開徵稿
出版型式 ,電子版,紙本
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機構典藏連結 ( http://tkuir.lib.tku.edu.tw:8080/dspace/handle/987654321/116022 )