(I,0) Mixed-valence state of a diiron complex with pertinence to the [FeFe]-hydrogenase active site: an IR, EPR, and computational study.
Biphenyl-2,2'-dithiolate (bpdt) bridged Fe(2)(bpdt)(CO)(6) (1) undergoes two sequential electrochemically quasi-reversible reductions. The one-electron reduction product 1(-) is unusually stable against irreversible structural changes and could be characterized by IR and EPR spectroscopy supported by computational methods. Reduction to the (I,0) state does not trigger bridging coordination of CO but partial deligation of the dithiolate in 1(-) that ultimately forms a diamagnetic dimerization product.
Singh
Pradyumna S
PS
Department of Photochemistry and Molecular Science, The Angstrom Laboratories, Uppsala University, BOX 532, 751 20 Uppsala, Sweden.
Rudbeck
Hans Christian
HC
Huang
Ping
P
Ezzaher
Salah
S
Eriksson
Lars
L
Stein
Matthias
M
Ott
Sascha
S
Lomoth
Reiner
R
D020134:Catalytic Domain; D004578:Electron Spin Resonance Spectroscopy; D005290:Ferric Compounds / Q000737:chemistry*; D006864:Hydrogenase / Q000737:chemistry* / Q000378:metabolism; D007506:Iron-Sulfur Proteins / Q000737:chemistry* / Q000378:metabolism; D008956:Models, Chemical; D013055:Spectrophotometry, Infrared
D005290:Ferric Compounds; D007506:Iron-Sulfur Proteins; C118830:iron hydrogenase; D006864:Hydrogenase