Dioxygen activation by a dinuclear thiolate-ligated Fe(ii) complex

Abstract

The activation of dioxygen by a dimeric Fe(ii) thiolate complex and the detection of an Fe(iii)–O2–Fe(iii) intermediate are reported.

Development of Nonheme {FeNO}7 Complexes Based on the Pyrococcus furiosus Rubredoxin for Red-Light-Controllable Nitric Oxide Release

“…Whereas in the presence of O 2 the photodecomposed protein (species C) showed characteristic spectra in both UV–vis absorption and EPR spectroscopies similar to those of pf Rd-C9A-Fe III (Figure A,B), surprisingly, its molecular weight was measured to be ∼16 Da larger (Figure C) than that of pf Rd-C9A-Fe III . It was considered that this species may be derived from the oxidation of Cys (S-oxygenation) or iron (Fe III -O 2 – , Fe III -O 2 2– , Fe IV/V O), as previously reported. ,− The reaction of species C with dimedonea reagent for the selective detection of S-oxygenates , was carried out, but no product was detected by ESI-MS (data not shown). Further, substoichiometric peroxynitrite was detected upon irradiation under air (Figure S16), which might be the product of the reaction between superoxide (O 2 – ) and the released NO, as reported for other iron peroxynitrite complexes. , We thus tend to assign species C as the Fe III -O 2 – complex, and at this stage, no further effort was made to elucidate the identity of this intermediate species.…”

Efficient Reduction of Dioxygen with Ferrocene Catalyzed by Thiocarbohydrazone Tetranuclear Cobalt(III) Coordination Compound

“…Comparing the length of these bonds with related bond lengths in hydrazone based ligands indicates that the lengths of these bonds are between the C-N and C=N bond lengths. [37] The lengths of C − S bonds are in the range of 1.759-1.776 Å which are within the normal range of C-S bonds, [38,39] indicating that this moiety adopts the thiol tautomeric form.…”

Oxoiron(IV)‐dominated Heterogeneous Fenton‐like Mechanism of Fe‐Doped MoS2

“…Compared to the prevalent nitrogen ligands [9] like porphyrin and its analogues, sulfur ligands [10] are also concerned because of the high reactivity of their corresponding Fe IV =O species. Hsieh et al [11] revealed the thiolate-ligated Fe IV -oxo species as the transient intermediate for the hydride-transfer reaction. Deutscher et al [12] revealed that introducing sulfur ligands to replace two equatorial nitrogen ligands weakens the Fe=O bond and thus enhances the oxidative reactivity of the Fe IV =O unit.…”

“…Compared to the prevalent nitrogen ligands [9] like porphyrin and its analogues, sulfur ligands [10] are also concerned because of the high reactivity of their corresponding Fe IV =O species. Hsieh et al [11] . revealed the thiolate‐ligated Fe IV ‐oxo species as the transient intermediate for the hydride‐transfer reaction.…”