Sulfur oxygenates of biomimetics of the diiron subsite of the [FeFe]-hydrogenase active site: properties and oxygen damage repair possibilities. Academic Article uri icon

abstract

  • This study explores the site specificity (sulfur vs the Fe-Fe bond) of oxygenation of diiron (Fe(I)Fe(I) and Fe(II)Fe(II)) organometallics that model the 2-iron subsite in the active site of [FeFe]-hydrogenase: (mu-pdt)[Fe(CO)(2)L][Fe(CO)(2)L'] (L = L' = CO (1); L = PPh(3), L' = CO (2); L = L' = PMe(3) (4)) and (mu-pdt)(mu-H)[Fe(CO)(2)PMe(3)](2) (5). DFT computations find that the Fe-Fe bond in the Fe(I)Fe(I) diiron models is thermodynamically favored to produce the mu-oxo or oxidative addition product, Fe(II)-O-Fe(II); nevertheless, the sulfur-based HOMO-1 accounts for the experimentally observed mono- and bis-O-atom adducts at sulfur, i.e., (mu-pst)[Fe(CO)(2)L][Fe(CO)(2)L'] (pst = -S(CH(2))(3)S(O)-, 1,3-propanesulfenatothiolate; L = L' = CO (1-O); L = PPh(3), L' = CO (2-O); L = L' = PMe(3) (4-O)) and (mu-pds)[Fe(CO)(2)L][Fe(CO)(2)L'] (pds = -(O)S(CH(2))(3)S(O)-, 1,3-propanedisulfenato; L = PPh(3), L' = CO (2-O(2))). The Fe(II)(mu-H)Fe(II) diiron model (5), for which the HOMO is largely of sulfur character, exclusively yields S-oxygenation. The depressing effect of such bridging ligand modification on the dynamic NMR properties arising from rotation of the Fe(CO)(3) correlates with higher barriers to the CO/PMe(3) exchange of (mu-pst)[Fe(CO)(3)](2) as compared to (mu-pdt)[Fe(CO)(3)](2). Five molecular structures are confirmed by X-ray diffraction: 1-O, 2-O, 2-O(2), 4-O, and 6. Deoxygenation with reclamation of the mu-pdt parent complex occurs in a proton/electron-coupled process. The possible biological relevance of oxygenation and deoxygenation studies is discussed.

published proceedings

  • J Am Chem Soc

author list (cited authors)

  • Liu, T., Li, B., Singleton, M. L., Hall, M. B., & Darensbourg, M. Y

citation count

  • 65

complete list of authors

  • Liu, Tianbiao||Li, Bin||Singleton, Michael L||Hall, Michael B||Darensbourg, Marcetta Y

publication date

  • June 2009