Bismercaptoethanediazacyclooctane as a N2S2 chelating agent and Cys-X-Cys mimic for Fe(NO) and Fe(NO)2.
The N-protonated bismercaptoethanediazacyclooctane serves as a bidentate dithiolate ligand to oxidized Fe(NO)(2) of Enemark-Feltam notation, E-F [Fe(NO)(2)],(9) mimicking Cys-X-Cys binding of Fe(NO)(2) to proteins or thio-biomolecules. The neutral compound is characterized by the well-known g = 2.03 EPR signal which is a hallmark of dinitrosyl iron complexes, DNIC's. The Fe(NO)(2) unit can be removed from the chelate by excess PhS(-), producing (PhS)(2)Fe(NO)(2)(-). Transfer of NO from Fe(H(+)bme-daco)(NO)(2) (nu(NO) = 1740, 1696 cm(-)(1)) to Fe(II) of [(bme-daco)Fe](2) yields the five-coordinate, square-pyramidal N(2)S(2)Fe(NO) (nu(NO) = 1649 cm(-)(1)), where NO is in the apical position. Its isotropic EPR signal at g = 2.05 is consistent with E-F [Fe(NO)](7) formulation. In excess NO, Roussin's red ester-type molecules are formed as dinuclear or tetranuclear species, [(micro-SRS)[Fe(2)(NO)(4)]](n)() (n =1, 2). These well-characterized molecules furnish reference points for positions and patterns in nu(NO) vibrational spectroscopy expected to be useful for in vivo studies of NO degradation of iron-sulfur clusters in ferredoxins.
Chiang
Chao-Yi
CY
Contribution from the Department of Chemistry, Texas A&M University, College Station, TX 77843, USA.
Miller
Matthew L
ML
Reibenspies
Joseph H
JH
Darensbourg
Marcetta Y
MY
D002614:Chelating Agents / Q000737:chemistry*; D018360:Crystallography, X-Ray; D034242:Cyclooctanes / Q000737:chemistry*; D003545:Cysteine / Q000031:analogs & derivatives* / Q000737:chemistry; D004578:Electron Spin Resonance Spectroscopy; D005290:Ferric Compounds / Q000737:chemistry*; D005296:Ferrous Compounds / Q000737:chemistry*; D015394:Molecular Structure; D009569:Nitric Oxide / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*
D002614:Chelating Agents; D034242:Cyclooctanes; D005290:Ferric Compounds; D005296:Ferrous Compounds; D013438:Sulfhydryl Compounds; D009569:Nitric Oxide; D003545:Cysteine