A [4Fe-4S] cluster dimer bridged by bis(2,2 '
| Autor: | Erwin P. L. van der Geer, Robertus J. M. Klein Gebbink, Gerard van Koten, Bart Hessen |
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| Přispěvatelé: | Molecular Inorganic Chemistry, Stratingh Institute of Chemistry |
| Jazyk: | angličtina |
| Rok vydání: | 2008 |
| Předmět: |
Spectrometry
Mass Electrospray Ionization Magnetic Resonance Spectroscopy SUBSITE-DIFFERENTIATED ANALOGS Stereochemistry Metal ions in aqueous solution Dimer FE4S4 CLUSTERS ELECTROCHEMICAL PROPERTIES MOLECULAR RECOGNITION Inorganic Chemistry chemistry.chemical_compound Molecular recognition TETRANUCLEAR CLUSTERS Cluster (physics) Ferrous Compounds Physical and Theoretical Chemistry BIS-TERPYRIDYL COMPLEXES biology Molecular Structure Bridging ligand Crystallography Cross-Linking Reagents chemistry Iron-sulfur protein CONVENIENT SYNTHESIS Spectrophotometry IRON-SULFUR PROTEINS biology.protein SPIN-STATE PROPERTIES ACTIVE-SITES Terpyridine Dimerization |
| Zdroj: | Inorganic Chemistry, 47(7), 2849-2857. AMER CHEMICAL SOC |
| ISSN: | 0020-1669 |
| Popis: | The use of 2,2':6',2"-terpyridine-4'-thiol (tpySH) was explored as a bridging ligand for the formation of stable. assemblies containing both [4Fe-4S] clusters and single metal ions. Reaction of tpySH (2 equiv) with (NH4)(2)Fe(SO4)(2)center dot 6H(2)O generated the homoleptic complex [Fe(tpySH)(2)](2+), which was isolated as its PF6- salt. The compound could be fully deprotonated to yield neutral [Fe(tpyS)(2)], and the absorption spectrum is highly dependent on the protonation state, Reaction of [Fe(tpySH)(2)](PF6)(2) with the new 3:1 site-differentiated cluster (n-Bu4N)(2)[Fe4S4(TriS)(SEt)] yielded the first metal-bridged [4Fe-4S] cluster dimer, (n-Bu4N)(2)[{Fe4S4(TriS)(mu-Stpy)}(2)Fe]. Electrochemical, studies indicate that the [4Fe-4S] clusters in the dimer act as independent redox units, while UV-vis spectroscopy provides strong evidence for a thioquinonoid electron distribution in the bridging tpyS(-) ligand. TpySH thus acts as a directional bridging ligand between [4Fe-4S] clusters and single metal ions, thereby opening the way to the synthesis of larger, more complex assemblies. |
| Databáze: | OpenAIRE |
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