Tetrahedral complexes containing the Fe(II)S4 core. The syntheses, ground-state electronic structures and crystal and molecular structures of the bis(tetraphenylphosphonium) tetrakis (thiophenolato)ferrate (II) and bis (tetrapheny lphosphonium) bis(dithiosquarato)ferrate (II) complexes. An analog for the active site in reducd rubredoxins (Rdred)

Coucouvanis, D.; Swenson, Dale C.; Baenziger, N. C.; Murphy, Clair; Holah, D. G.; Sfarnas, N.; Simopoulos, A.; Kostikas, A.

doi:10.1021/ja00402a020

Cited by 126 publications

(86 citation statements)

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“…Mössbauer spectroscopy has been employed in studies of the Fe II S 4 ‐containing centers of inorganic complexes and the active site of rubredoxin . The zero‐field Mössbauer spectra of powder samples of 1 and 2 at 80 K are shown in Figure .…”

Section: Resultsmentioning

confidence: 99%

Investigating the Structural, Spectroscopic, and Electrochemical Properties of [Fe{(EPiPr₂)₂N}₂] (E = S, Se) and the Formation of Iron Selenides by Chemical Vapor Deposition

et al. 2016

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The anionic L = [(EPiPr2)2N]– (E = S, Se) form of the dichalcogenidoimidodiphosphinato‐type ligands containing iPr peripheral groups has been shown previously to afford tetrahedral [MIIL2] complexes (E = S, M = Mn, Co, Ni, Zn; E = Se, M = Co, Ni, Zn). The syntheses of the analogous [FeL2] complexes [E = S (1), Se (2)] were performed in this work through metathesis reactions between FeCl2 and the corresponding KL salts. For both 1 and 2, X‐ray crystallography revealed two distinct molecules in the asymmetric unit. Complexes 1 and 2 are isostructural and exhibit P–E and P–N bond‐length differences compared with those of the free ligands, and these differences are translated into shifts of the corresponding IR bands. Cyclic voltammetry studies showed that the FeII → FeIII oxidation in 2 occurs at a lower potential than that of 1. The zero‐field Mössbauer spectra of the two complexes are quite similar and provide evidence of similar S = 2 electronic structures. The observation of crystallographically distinct FeIIE4 sites for both 1 and 2 is also revealed in the corresponding Mössbauer spectra. Complex 2 was employed as a single‐source precursor in catalyst‐aided chemical vapor deposition experiments, which afforded the iron selenides FeSe and Fe3Se4.

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Section: Resultsmentioning

confidence: 99%

Investigating the Structural, Spectroscopic, and Electrochemical Properties of [Fe{(EPiPr₂)₂N}₂] (E = S, Se) and the Formation of Iron Selenides by Chemical Vapor Deposition

et al. 2016

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“…The three open-shell, mononuclear complexes studied, [Fe(SEt) 4 ] − (S = 5/2) and the two S = 2 Fe 2+ complexes [Fe(S 4 C 8 O 4 )] 2− and [Fe(SPh) 4 ] 2− , may be regarded as synthetic analogues of the oxidized and the reduced forms of the [Fe(SR) 4 ] center of bacterial rubredoxins 40,41,42. The three antiferromagnetically coupled diferric complexes [Fe 2 S 2 (S 2 - o -xyl) 2 ] 2− ,43,44,45 [Fe 2 S 2 (OPh- p -CH 3 ) 4 ] 2− ,45 and [Fe 2 S 2 (C 4 H 4 N) 4 ] 2− ,45 were originally prepared as models for plant-type 2Fe-2S ferredoxins and Rieske proteins 45,46,47.…”

Section: Resultsmentioning

confidence: 99%

Density Functional Theory Calculations on Mössbauer Parameters of Nonheme Iron Nitrosyls

2009

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DFT calculations on transition metal nitrosyls often reveal unusual spin density profiles, involving substantial spatial separation of majority and minority spin densities. Against this context, there is a significant lack of studies where DFT calculations have been quantitatively calibrated against experimental spectroscopic properties. Reported herein are DFT calculations of Mössbauer isomer shifts and quadrupole splittings for 21 nonheme iron complexes (26 distinct iron sites) including 9 iron nitrosyls. Low-(S = 1/2) and high-spin (S = 3/2) {FeNO} 7 complexes, S = 1/2 {Fe(NO) 2 } 9 species, and polynuclear iron nitrosyls are all represented within the set of compounds examined. The general conclusion with respect to isomer shifts is that DFT (OLYP/STO-TZP) performs comparably well for iron nitrosyls and for iron complexes in general. However, quadrupole splittings are less accurately reproduced for nitrosyl complexes.

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“…The inclusion of the two bulky

{PPh}_{4}^{4 +}

counter-ions PTSQFE10 co-crystallized with

Fe {false(DTSQ false)}_{2}^{2 -}

typically did not alleviate the problem (only M06-2X produced a slight improvement). There is another compound in our data set taken from the same paper where

Fe {false(DTSQ false)}_{2}^{2 -}

was originally described along with its Mössbauer and X-ray data87

- Fe {false(SPh false)}_{4}^{2 -}

(PTHPFE10). Its computed QS is in an excellent agreement with the experimental value.…”

Section: Quadrupole Splittingmentioning

confidence: 99%

Prediction of ⁵⁷Fe Mössbauer Parameters by Density Functional Theory: A Benchmark Study

Bochevarov

Friesner

Lippard

2010

J. Chem. Theory Comput.

130

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We report the performance of eight density functionals (B3LYP, BPW91, OLYP, O3LYP, M06, M06-2X, PBE, and SVWN5) in two Gaussian basis sets (Wachters and Partridge-1 on iron atoms; cc-pVDZ on the rest of atoms) for the prediction of the isomer shift (IS) and the quadrupole splitting (QS) parameters of Mössbauer spectroscopy. Two sources of geometry (density functional theory-optimized and X-ray) are used. Our data set consists of 31 iron-containing compounds (35 signals), the Mössbauer spectra of which were determined at liquid helium temperature and where the X-ray geometries are known. Our results indicate that the larger and uncontracted Partridge-1 basis set produces slightly more accurate linear correlations of electronic density used for the prediction of IS and noticeably more accurate results for the QS parameter. We confirm and discuss the earlier observation of Noodleman and co-workers that different oxidation states of iron produce different IS calibration lines. The B3LYP and O3LYP functionals have the lowest errors for either IS or QS. BPW91, OLYP, PBE, and M06 have a mixed success whereas SVWN5 and M06-2X demonstrate the worst performance. Finally, our calibrations and conclusions regarding the best functional to compute the Mössbauer characteristics are applied to candidate structures for the peroxo and Q intermediates of the enzyme methane monooxygenase hydroxylase (MMOH), and compared to experimental data in the literature.

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Cited by 126 publications

References 2 publications

Investigating the Structural, Spectroscopic, and Electrochemical Properties of [Fe{(EPiPr₂)₂N}₂] (E = S, Se) and the Formation of Iron Selenides by Chemical Vapor Deposition

Investigating the Structural, Spectroscopic, and Electrochemical Properties of [Fe{(EPiPr₂)₂N}₂] (E = S, Se) and the Formation of Iron Selenides by Chemical Vapor Deposition

Density Functional Theory Calculations on Mössbauer Parameters of Nonheme Iron Nitrosyls

Prediction of ⁵⁷Fe Mössbauer Parameters by Density Functional Theory: A Benchmark Study

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Cited by 126 publications

References 2 publications

Investigating the Structural, Spectroscopic, and Electrochemical Properties of [Fe{(EPiPr2)2N}2] (E = S, Se) and the Formation of Iron Selenides by Chemical Vapor Deposition

Investigating the Structural, Spectroscopic, and Electrochemical Properties of [Fe{(EPiPr2)2N}2] (E = S, Se) and the Formation of Iron Selenides by Chemical Vapor Deposition

Density Functional Theory Calculations on Mössbauer Parameters of Nonheme Iron Nitrosyls

Prediction of 57Fe Mössbauer Parameters by Density Functional Theory: A Benchmark Study

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Investigating the Structural, Spectroscopic, and Electrochemical Properties of [Fe{(EPiPr₂)₂N}₂] (E = S, Se) and the Formation of Iron Selenides by Chemical Vapor Deposition

Investigating the Structural, Spectroscopic, and Electrochemical Properties of [Fe{(EPiPr₂)₂N}₂] (E = S, Se) and the Formation of Iron Selenides by Chemical Vapor Deposition

Prediction of ⁵⁷Fe Mössbauer Parameters by Density Functional Theory: A Benchmark Study