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Pendant bases as proton transfer relays in diiron dithiolate complexes inspired by [Fe-Fe] hydrogenase active site

Release Time:2019-03-10  Hits:

Indexed by: Journal Article

Date of Publication: 2008-08-15

Journal: JOURNAL OF ORGANOMETALLIC CHEMISTRY

Included Journals: Scopus、EI、SCIE

Volume: 693

Issue: 17

Page Number: 2828-2834

ISSN: 0022-328X

Key Words: pendant base; phosphine ligand exchange; proton transfer; [Fe-Fe] hydrogenase

Abstract: 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.

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