Change search
ReferencesLink to record
Permanent link

Direct link
Binuclear iron-sulfur complexes with bidentate phosphine ligands as active site models of Fe-hydrogenase and their catalytic proton reduction
Show others and affiliations
2007 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 46, no 6, 1981-1991 p.Article in journal (Refereed) Published
Abstract [en]

The displacement of CO in a few simple Fe(I)-Fe(I) hydrogenase model complexes by bisphosphine ligands Ph2P-(CH2)(n)-PPh2 [with n = 1 (dppm) or n = 2 (dppe)] is described. The reaction of [{mu-(SCH2)(2)CH2}Fe-2(CO)(6)] (1) and [{mu-(SCH2)(2)N(CH2CH2CH3)}Fe-2(CO)(6)] (2) with dppe gave double butterfly complexes [{mu-(SCH2)(2)CH2}Fe-2(CO)(5)(Ph2PCH2)](2) (3) and [{mu-(SCH2)(2)N(CH2CH2CH3)}Fe-2(CO)(5)(Ph2PCH2)](2) (4), where two Fe2S2 units are linked by the bisphosphine. In addition, an unexpected byproduct, [{mu-(SCH2)(2)N(CH2CH2CH3)}Fe-2(CO)(5){Ph2PCH2CH2(Ph2PS)}] (5), was isolated when 2 was used as a substrate, where only one phosphorus atom of dppe is coordinated, while the other has been converted to PS, presumably by nucleophilic attack on bridging sulfur. By contrast, the reaction of 1 and 2 with dppm under mild conditions gave only complexes [{mu-(SCH2)(2)CH2}Fe-2(CO)(5)(Ph2PCH2PPh2)] (6) and [{mu-(SCH2)(2)N(CH2CH2CH3)}Fe-2(CO)(5)(Ph2PCH2PPh2)] (8), where one ligand coordinated in a monodentate fashion to one Fe2S2 unit. Furthermore, under forcing conditions, the complexes [{mu-(SCH2)(2)CH2}Fe-2(CO)(4){mu-(Ph2P)(2)CH2}] (7) and [{mu-(SCH2)(2)N(CH2CH2CH3)}Fe-2(CO)(4){mu-(Ph2P)(2)CH2}] (9) were formed, where the phosphine acts as a bidentate ligand, binding to both the iron atoms in the same molecular unit. Electrochemical studies show that the complexes 3, 4, and 9 catalyze the reduction of protons to molecular hydrogen, with 4 electrolyzed already at -1.40 V versus Ag/AgNO3 (-1.0 V vs NHE).

Place, publisher, year, edition, pages
2007. Vol. 46, no 6, 1981-1991 p.
National Category
Chemical Sciences
URN: urn:nbn:se:kth:diva-37015DOI: 10.1021/ic0610278ISI: 000244798800017PubMedID: 17295467ScopusID: 2-s2.0-34047145454OAI: diva2:431832
Available from: 2011-07-26 Created: 2011-07-26 Last updated: 2011-07-26Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full textPubMedScopus

Search in DiVA

By author/editor
Sun, Licheng
By organisation
Organic Chemistry
In the same journal
Inorganic Chemistry
Chemical Sciences

Search outside of DiVA

GoogleGoogle Scholar
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

Altmetric score

Total: 17 hits
ReferencesLink to record
Permanent link

Direct link