1017610-28-4Relevant articles and documents
Investigations on the active site models of [FeFe]-hydrogenases: synthesis, structure, and properties of N-functionalized azadithiolatodiiron complexes containing mono- And diphosphine ligands
Song, Li-Cheng,Wang, Hu-Ting,Ge, Jian-Hua,Mei, Shu-Zhen,Gao, Jie,Wang, Liang-Xing,Gai, Bin,Zhao, Li-Qun,Yan, Jing,Wang, Yong-Zhen
, p. 1409 - 1416 (2009/02/01)
As the new H-cluster models, a series of N-functionalized azadithiolatodiiron complexes containing mono- and diphosphine ligands 1-7 have been prepared by various methods from complexes [μ-SCH2N(FUn)] Fe2(CO)6 (A, Fun=C6H4CHO-p; B, Fun=C6H4CO2Me-p; C, Fun=CH2CH 2O2CCH2C10H7-1; D, Fun = CH2CH2OH) and [(μ-SCH2)2N(FUn)] Fe2(CO)5(Ph2PH) (E, Fun = C6H 4OMe-p). Treatment of A and B with 1 equiv of Me3NO · 2H2O followed by 1 equiv of Ph3P or Ph 2PH affords the corresponding monophosphine-substituted complexes [(μ-SCH2)2N(C6H4CHO-p)]Fe 2(CO)5(Ph3P) (1) and [(μ-SCH 2)2N(C6H4CO2Me-P)]Fe2(CO) 5L (2, L = Ph3P; 3, Ph2PH). Further treatment of B with ca. 1 equiv of Ph2PC2H4PPh 2 (dppe) produced the diphosphine dppe-bridged single model [(μ-SCH2)2N(C6H4CO 2caret;Me-p)]Fe2(CO)4(dppe) (4), whereas C reacts with 1 equiv of Me3NO · 2H2O followed by 0.5 equiv of (η5-Ph2PC5H4) 2Fe (dppf) to give the diphosphine dppf-bridged double model [(μ-SCH2)2N(CH2CH2O 2CCH2C10H7-1)Fe2(CO) 5]2(dppf) (5). While D reacts with 1 equiv of w-BuLi followed by 1 equiv of Ph2PCl or directly reacts with 1 equiv of Ph2PCl in the presence of Et3N to generate N-alkoxyphosphine-substituted complex [CM-SCH2)2N(CH 2CH2OPPh2-η1)]Fe 2(CO)5 (6), treatment of E with 1 equiv of n-BuLi followed by 1 equiv of CpFe(CO)2I yields organometallic phosphine-substituted complex [μ-SCH2)2N(C6H4OMe-P)] Fe2(CO)5[Ph2PFe(CO)2Cp] (7). AU the new model complexes 1-7 are fully characterized by elemental analysis, spectroscopy, and particularly for 1, 3, 4, 6, and 7 X-ray crystallography. More interestingly, 2 is found to be a catalyst for HOAc proton reduction to hydrogen under CV conditions. In addition, according to electrochemical and spectroelectrochemical studies, an ECEC mechanism is proposed for this electrocatalytic reaction.