期刊論文
| 學年 | 99 |
|---|---|
| 學期 | 1 |
| 出版（發表）日期 | 2010-10-01 |
| 作品名稱 | A {Fe(NO)3}10 Trinitrosyliron Complex Stabilized by an N-Heterocyclic Carbene and the Cationic and Neutral {Fe(NO)2}9/10 Products of Its NO Release |
| 作品名稱（其他語言） | |
| 著者 | Hsieh, Chung-Hung; Darensbourg Marcetta Y. |
| 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 | Journal of the American Chemical Society 132(40), pp.14118-14125 |
| 摘要 | In contrast to the instability of XFe(NO)3 and [R3PFe(NO)3]+, the N-heterocyclic carbene (NHC)-containing trinitrosyliron complex (TNIC) [(IMes)Fe(NO)3][BF4] (1) [IMes =1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene] can be readily isolated and manipulated in solution under ambient conditions. Nevertheless, in the presence of thiolates (SR−), this EPR-silent TNIC (denoted {Fe(NO)3}10 in the Enemark−Feltham notation) releases gaseous NO, affording in the case of SR− = SPh− the EPR-active, neutral dinitrosyliron complex (DNIC) (IMes)Fe(SPh)(NO)2 (3, {Fe(NO)2}9). Carbon monoxide enforces a bimolecular reductive elimination of PhSSPh from 3, yielding (IMes)(CO)Fe(NO)2 (2), a reduced {Fe(NO)2}10 DNIC. The NO released from TNIC 1 in the presence of SPh− could be taken up by the NO-trapping agent [(bme-dach)Fe]2 [bme-dach = N,N′-bis(2-mercaptoethyl)-1,4-diazacycloheptane] to form the mononitrosyliron complex (MNIC) (bme-dach)Fe(NO). In the absence of SPh−, direct mixing of [(bme-dach)Fe]2 with 1 releases both NO and the NHC with formation of a spin-coupled, diamagnetic {Fe(NO)}7−{Fe(NO)2}9 complex, [(NO)Fe(bme-dach)Fe(NO)2][BF4] (4). In 4, the MNIC serves as a bidentate metallodithiolate ligand of Fe(NO)2, forming a butterfly complex in which the Fe−Fe distance is 2.7857(8) Å. Thus, 1 is found to be a reliable synthon for [{Fe(NO)2}9]+. The solid-state molecular structures of complexes 1−3 show that all three complexes have a tetrahedral geometry in which the bulky mesitylene substituents of the carbene ligand appear to umbrella the Fe(NO)2L [L = NO (1), CO (2), SPh (3)] motif. |
| 關鍵字 | |
| 語言 | en |
| ISSN | 0002-7863 1520-5126 |
| 期刊性質 | 國外 |
| 收錄於 | |
| 產學合作 | |
| 通訊作者 | Darensbourg Marcetta Y. |
| 審稿制度 | 是 |
| 國別 | USA |
| 公開徵稿 | |
| 出版型式 | 紙本 電子版 |
| 相關連結 |
機構典藏連結 ( http://tkuir.lib.tku.edu.tw:8080/dspace/handle/987654321/97568 ) |