Evidence for the formation of terminal hydrides by protonation of an asymmetric iron hydrogenase active site mimic.
Treatment of [Fe2(mu-pdt)(CO)6] [pdt=S(CH2)3S] with dppe (Ph2PCH2CH2PPh2) in refluxing toluene affords the asymmetric complex [Fe2(mu-pdt)(CO)4(dppe)] (1). Protonation of 1 with HBF4-Et2O in CH2Cl2 gives at room temperature the mu-hydrido derivative [Fe2(mu-pdt)(CO)4(dppe)(mu-H)](BF4) (2). Monitoring the reaction by 1H, 31P, and 13C NMR at low temperature reveals unambiguously that the process of the protonation of 1 implies terminal hydride intermediates.
Ezzaher
Salah
S
Chimie, Electrochimie Moléculaires et Chimie Analytique, Faculté des Sciences, UMR CNRS 6521, Université de Bretagne Occidentale, 6 Avenue Le Gorgeu, CS 93837, 29238 Brest Cedex 3, France.
Capon
Jean-François
JF
Gloaguen
Frédéric
F
Pétillon
François Y
FY
Schollhammer
Philippe
P
Talarmin
Jean
J
Pichon
Roger
R
Kervarec
Nelly
N
D001665:Binding Sites; D040761:Biomimetic Materials / Q000737:chemistry* / Q000378:metabolism*; D006864:Hydrogenase / Q000737:chemistry*; D007506:Iron-Sulfur Proteins / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D011522:Protons; D013237:Stereoisomerism; D013696:Temperature; D014867:Water / Q000737:chemistry
D007506:Iron-Sulfur Proteins; D011522:Protons; D014867:Water; C118830:iron hydrogenase; D006864:Hydrogenase