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论文类型：期刊论文

发表时间：2008-08-15

发表刊物：JOURNAL OF ORGANOMETALLIC CHEMISTRY

收录刊物：SCIE、EI、Scopus

卷号：693

期号：17

页面范围：2828-2834

ISSN号：0022-328X

关键字：pendant base; phosphine ligand exchange; proton transfer; [Fe-Fe] hydrogenase

摘要：Three dinuclear iron complexes containing pendant nitrogen bases in phosphine ligands with general formular ( l- pdt) [ Fe2( CO) 5L] ( where pdt is SCH2CH2CH2S, L = PPh2NH( CH2) 2N( CH3) 2 ( 5), PPh2NH( 2- NH2C6H4) ( 6), PPh2[ 2- N( CH3) 2CH2C6H4] ( 7)), were prepared as the models of the [ Fe - Fe] hydrogenase active site. The molecular structures of 5 - 7 were characterized by X- ray crystallography. The secondary amine in 6 has weak intramolecular hydrogen bonding with both the terminal nitrogen and sulfur atom, which may suggest a proton transfer pathway from amine in phosphine ligand to the sulfur atom of active site. Protonation of complexes 5 and 6 only occurred at the terminal nitrogen atom. Electrochemical properties of the complexes were studied in the presence of tri. ic acid by cyclic voltammetry. (c) 2008 Published by Elsevier B. V.