期刊論文
| 學年 | 101 |
|---|---|
| 學期 | 2 |
| 出版（發表）日期 | 2013-06-01 |
| 作品名稱 | Carbon Monoxide Induced Reductive Elimination of Disulfide in an N-Heterocyclic Carbene (NHC)/ Thiolate Dinitrosyl Iron Complex (DNIC) |
| 作品名稱（其他語言） | |
| 著者 | Pulukkody, Randara; Kyran, Samuel J.; Bethel, Ryan D.; Hsieh, Chung-Hung; Hall, Michael B.; Darensbourg, Donald J.; 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 135(22), pp.8423-8430 |
| 摘要 | Dinitrosyliron complexes (DNICs) are organometallic-like compounds of biological significance in that they appear in vivo as products of NO degradation of iron–sulfur clusters; synthetic analogues have potential as NO storage and releasing agents. Their reactivity is expected to depend on ancillary ligands and the redox level of the distinctive Fe(NO)2 unit: paramagnetic {Fe(NO)2}9, diamagnetic dimerized forms of {Fe(NO)2}9 and diamagnetic {Fe(NO)2}10 DNICs (Enemark–Feltham notation). The typical biological ligands cysteine and glutathione themselves are subject to thiolate-disulfide redox processes, which when coupled to DNICs may lead to intricate redox processes involving iron, NO, and RS–/RS•. Making use of an N-heterocyclic carbene-stabilized DNIC, (NHC)(RS)Fe(NO)2, we have explored the DNIC-promoted RS–/RS• oxidation in the presence of added CO wherein oxidized {Fe(NO)2}9 is reduced to {Fe(NO)2}10 through carbon monoxide (CO)/RS• ligand substitution. Kinetic studies indicate a bimolecular process, rate = k [Fe(NO)2]1[CO]1, and activation parameters derived from kobs dependence on temperature similarly indicate an associative mechanism. This mechanism is further defined by density functional theory computations. Computational results indicate a unique role for the delocalized frontier molecular orbitals of the Fe(NO)2 unit, permitting ligand exchange of RS• and CO through an initial side-on approach of CO to the electron-rich N–Fe–N site, ultimately resulting in a 5-coordinate, 19-electron intermediate with elongated Fe–SR bond and with the NO ligands accommodating the excess charge. |
| 關鍵字 | |
| 語言 | en_US |
| ISSN | 0002-7863 |
| 期刊性質 | 國外 |
| 收錄於 | SCI |
| 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 |
| 相關連結 |
機構典藏連結 ( http://tkuir.lib.tku.edu.tw:8080/dspace/handle/987654321/97540 ) |