期刊
RSC ADVANCES
卷 5, 期 37, 页码 29022-29031出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c4ra15150j
关键词
-
资金
- National Natural Science Foundation of China [21103121, 21276187]
- Research Fund for the Doctoral Program of Higher Education of China [20110032120011]
- Tianjin Municipal Natural Science Foundation [13JCQNJC05800]
(mu-dmedt)[Fe(CO)(3)](2) (I, dmedt = 2,3-butanedithiol) was chosen as the parent complex. A series of new model complexes, N-heterocyclic carbene (NHC) substituted (mu-dmedt)[Fe-Fe]-NHC (II, (mu-dmedt) [Fe(CO)(2)](2)[I-Me(CH2)(2)I-Me], I-Me = 1-methylimidazol-2-ylidene; III, {(mu-dmedt)[Fe-2(CO)(5)]}(2)[I-Me(CH2)(2)I-Me]; IV, (mu-dmedt)[Fe-2(CO)(5)]IMes, IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; V, (mu-dmedt) [Fe-2(CO)(5)]IMe, IMe = 1,3-dimethylimidazol-2-ylidene) as mimics of the [Fe-Fe]-H(2)ase active site were synthesized from I and characterized using solution IR spectroscopy, NMR spectroscopy, elemental analysis and single-crystal X-ray diffraction. The electrochemical properties of complexes I-V, with and without the addition of HOAc, were investigated by cyclic voltammetry in the coordinating solvent CH3CN to evaluate the effects of different NHC ligands on the redox properties of the iron atoms of the series of complexes. It was concluded that all the new complexes are electrochemical catalysts for proton reduction to hydrogen. The symmetrically substituted cisoid basal/basal coordination complex II displays the most negative reduction potential owing to the stronger delta-donating ability of the NHC and the orientation of the NHC donor carbon as a result of the constraints of the bridging bidentate ligands. A new application for the [Fe-Fe]-NHC model complexes in the direct catalytic hydroxylation of benzene to phenol was also studied. Under the optimized experimental conditions (II, 0.01 mmol; benzene, 0.1 mL; CH3CN, 2.0 mL; H2O2, 6.0 mmol; 60 degrees C, 3 h), the maximal phenol yield was 26.7%.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据