Hydrogen-atom and oxygen-atom transfer reactivities of iron(iv)-oxo complexes of quinoline-substituted pentadentate ligands
Munshi, S., Sinha, A., Yiga, S., Banerjee, S., Singh, R., Hossain, M. K., Haukka, M., Valiati, A. F., Huelsmann, R. D., Martendal, E., Peralta, R., Xavier, F., Wendt, O. F., Paine, T. K., & Nordlander, E. (2022). Hydrogen-atom and oxygen-atom transfer reactivities of iron(iv)-oxo complexes of quinoline-substituted pentadentate ligands. Dalton Transactions, 51(3), 870-884. https://doi.org/10.1039/d1dt03381f
Published inDalton Transactions
DisciplineEpäorgaaninen kemiaEpäorgaaninen ja analyyttinen kemiaInorganic ChemistryInorganic and Analytical Chemistry
© 2022 Royal Society of Chemistry
A series of iron(II) complexes with the general formula [FeII(L2-Qn)(L)]n+ (n = 1, L = F−, Cl−; n = 2, L = NCMe, H2O) have been isolated and characterized. The X-ray crystallographic data reveals that metal–ligand bond distances vary with varying ligand field strengths of the sixth ligand. While the complexes with fluoride, chloride and water as axial ligand are high spin, the acetonitrile-coordinated complex is in a mixed spin state. The steric bulk of the quinoline moieties forces the axial ligands to deviate from the Fe–Naxial axis. A higher deviation/tilt is noted for the high spin complexes, while the acetonitrile coordinated complex displays least deviation. This deviation from linearity is slightly less in the analogous low-spin iron(II) complex [FeII(L1-Qn)(NCMe)]2+ of the related asymmetric ligand L1-Qn due to the presence of only one sterically demanding quinoline moiety. The two iron(II)-acetonitrile complexes [FeII(L2-Qn)(NCMe)]2+ and [FeII(L1-Qn)(NCMe)]2+ generate the corresponding iron(IV)-oxo species with higher thermal stability of the species supported by the L1-Qn ligand. The crystallographic and spectroscopic data for [FeIV(O)(L1-Qn)](ClO4)2 bear resemblance to other crystallographically characterized S = 1 iron(IV)-oxo complexes. The hydrogen atom transfer (HAT) and oxygen atom transfer (OAT) reactivities of both the iron(IV)-oxo complexes were investigated, and a Box–Behnken multivariate optimization of the parameters for catalytic oxidation of cyclohexane by [FeII(L2-Qn)(NCMe)]2+ using hydrogen peroxide as the terminal oxidant is presented. An increase in the average Fe–N bond length in [FeII(L1-Qn)(NCMe)]2+ is also manifested in higher HAT and OAT rates relative to the other reported complexes of ligands based on the N4Py framework. The results reported here confirm that the steric influence of the ligand environment is of critical importance for the reactivity of iron(IV)-oxo complexes, but additional electronic factors must influence the reactivity of iron-oxo complexes of N4Py derivatives. ...
PublisherRoyal Society of Chemistry (RSC)
ISSN Search the Publication Forum1477-9226
Publication in research information system
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Additional information about fundingTKP acknowledges the Science and Engineering Research Board (SERB), India, for financial support (project: CRG/2019/ 006393). SM and SB thank the Council of Scientific and Industrial Research (CSIR), India, for research fellowships. The financial support from the Technical Research Center (TRC) at IACS for setting up a Mössbauer spectrometer facility is thankfully acknowledged. AS thanks the Carl Trygger Foundation for a postdoctoral fellowship. MKH thanks the European Commission for an Erasmus Mundus predoctoral fellowship. SY and OFW thank the Swedish Research Council and the SIDA bilateral support program for financial support. FX and EM thank FAPESC for financial support. RA, FX and EN thank CAPES and STINT for a Swedish-Brazilian Joint Collaboration Grant. ...
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