期刊論文
| 學年 | 87 |
|---|---|
| 學期 | 1 |
| 出版（發表）日期 | 1999-01-01 |
| 作品名稱 | A five-coordinate, sixteen-electron manganese(I) complex [Mn(CO)3(S,S–C6H4)]– stabilized by S,S π-donation from chelating [S,S–C6H4]2– |
| 作品名稱（其他語言） | |
| 著者 | Lee, Chien-Ming; Lin, Ging-Yi; Hsieh, Chung-Hung; Hu, Ching-Han; Lee, Gene-Hsiang; Peng, Shie-Ming; Liaw, Wen-Feng |
| 單位 | 淡江大學化學學系 |
| 出版者 | Cambridge: R S C Publications |
| 著錄名稱、卷期、頁數 | Journal of the Chemical Society, Dalton Transactions 1999(14), pp.2393-2398 |
| 摘要 | The five-coordinate, sixteen-electron manganese(I) complex [N(PPh3)2][Mn(CO)3(S,S–C6H4)] 1 was prepared from reaction of [N(PPh3)2][Mn(CO)3(NH,S–C6H4)] and 1,2-benzenedithiol via the hexacoordinate intermediate fac-[Mn(CO)3(S–C6H4SH)(NH2,S–C6H4)]–. Alternatively, oxidative addition of 1,2-benzenedithiol to [Mn(CO)5]–, followed by a Lewis acid–base reaction, with evolution of H2 gas (identified by gas chromatography), led to formation of the coordinatively-unsaturated complex 1. In contrast, reaction of bis(2-pyridyl) disulfide and [N(PPh3)2][Mn(CO)5] afforded hexacoordinate fac-[N(PPh3)2][Mn(CO)3(S–C5H4–N)(S–C5H4N)] 2, with one anionic [S–C5H4N]– ligand bound to MnI in a monodentate (S-bonded) manner and the other [S–C5H4–N]– ligand bound in a bidentate manner (S,N-bonded). Complexes 1 and 2 have been characterized in solution by infrared spectroscopy and in the solid state by X-ray crystallography. The strong π-donating ability of the bidentate [S,S–C6H4]2– ligand stabilizes the unsaturated complex 1 which has short MnI–S bond lengths of 2.230(1) Å (average) as a result. The existence of one π and two σ bonds between the [Mn(CO)3]+ and [S,S–C6H4]2– fragments, based on qualitative frontier molecular orbital analysis, also indicates that the lone-pair electrons are delocalized around the sulfur-manganese-sulfur system stabilizing the five-coordinate complex 1. The IR carbonyl stretching frequencies and the MnI–S bond distances of complexes 1 and [N(PPh3)2][Mn(CO)3(NH,S–C6H4)] suggest that the relative π-donating ability of the bidentate ligands is [NH,S–C6H4]2– > [S,S–C6H4]2–. The Mulliken atomic charges derived from Hartree–Fock calculations roughly quantify the charge distribution in the complex [Mn(CO)3(NH,S–C6H4)]– (δ(N) = –1.14; δ(S) = –0.43; δ(Mn) = 1.14), and supports the premise that the reactions of [Mn(CO)3(NH,S–C6H4)]– with electrophiles (1,2-benzenedithiol, thiophene-2-thiol, 1,2-ethanedithiol) occur at the more electron-rich amide site, yielding charge-controlled, collision complexes. |
| 關鍵字 | |
| 語言 | en |
| ISSN | 1472-7773 1364-5447 |
| 期刊性質 | 國外 |
| 收錄於 | |
| 產學合作 | |
| 通訊作者 | |
| 審稿制度 | 是 |
| 國別 | GBR |
| 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/987654321/97589 ) |