Hydrogen activation by biomimetic diiron dithiolates.
Using the thermally stable salts of [Fe(2)(SR)(2)(CO)(3)(PMe(3))(dppv)]BAr(F)(4), we found that the azadithiolates [Fe(2)(adtR)(CO)(3)(PMe(3))(dppv)](+) react with high pressures of H(2) to give the hydride [Fe(2)(mu-H)(adtR)(CO)(3)(dppv)(PMe(3))]BAr(F)(4). The related oxadithiolate and propanedithiolate complexes are unreactive toward H(2). Molecular hydrogen is proposed to undergo heterolysis assisted by the amine followed by isomerization of an initially formed terminal hydride. Use of H(2) and D(2)O gave the deuteride as well as the hydride, implicating protic intermediates.
Olsen
Matthew T
MT
Department of Chemistry, University of Illinois, Urbana, Illinois 61801, USA.
Barton
Bryan E
BE
Rauchfuss
Thomas B
TB
D040761:Biomimetic Materials / Q000737:chemistry* / Q000378:metabolism; D005290:Ferric Compounds / Q000737:chemistry* / Q000378:metabolism; D006859:Hydrogen / Q000737:chemistry* / Q000378:metabolism; D006864:Hydrogenase / Q000378:metabolism; D007506:Iron-Sulfur Proteins / Q000378:metabolism; D013438:Sulfhydryl Compounds / Q000737:chemistry* / Q000378:metabolism; D013816:Thermodynamics
D005290:Ferric Compounds; D007506:Iron-Sulfur Proteins; D013438:Sulfhydryl Compounds; C002007:dithiol-iron(III)-sulfide complex; D006859:Hydrogen; C118830:iron hydrogenase; D006864:Hydrogenase