A new cumulene diiron complex related to the active site of Fe-only hydrogenases and its phosphine substituted derivatives: synthesis, electrochemistry and structural characterization |
| |
Authors: | Wen Na Xu Fenfen Feng Yanan Du Shaowu |
| |
Affiliation: | a State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, PR Chinab Graduate University of Chinese Academy of Sciences, Beijing 100039, PR China |
| |
Abstract: | A new cumulene diiron complex related to the Fe-only hydrogenase active site [(μ-SCH2C(S)CCH2)Fe2(CO)6] (1) was obtained by treatment of (μ-LiS)2Fe2(CO)6 with excess 1,4-dichloro-2-butyne. By controllable CO displacement of 1 with PPh3 and bis(diphenylphosphino)methane (dppm), mono- and di-substituted complexes, namely [(μ-SCH2C(S)CCH2)Fe2(CO)5L] (2: L = PPh3; 3: L = dppm) and [(μ-SCH2C(S)CCH2)Fe2(CO)4L2] (4: L = PPh3; 5: L = dppm) could be prepared in moderate yields. Treatment of 1 with bis(diphenylphosphino)ethane (dppe) afforded a double butterfly complex [(μ-SCH2C(S)CCH2)Fe2(CO)5]2(μ-dppe) (7). With dppm in refluxing toluene, a dppm-bridged complex [(μ-SCH2C(S)CCH2)Fe2(CO)4(μ-dppm)] (6) was obtained. These model complexes were characterized by IR, 1H, 31P NMR spectra and the molecular structures of 1, 2 and 5-7 were determined by single crystal X-ray analyses. The electrochemistry of 1-3 was studied and the electrocatalytic property of 1 was investigated for proton reduction in the presence of HOAc. |
| |
Keywords: | Bioinorganic chemistry Iron hydrogenase Diiron dithiolato complexes Cumulene |
本文献已被 ScienceDirect PubMed 等数据库收录! |
|