Home Übergangsmetallkomplexe mit Schwefelliganden, CXXXIII [1]. Synthese, Struktur und Eigenschaften neuer FeII-Komplexe mit [FeN2S2]-Gerüsten / Transition Metal Complexes with Sulfur Ligands, CXXXIII [1]. Synthesis, Structure, and Properties of New FeII Complexes with [Fe2N2S2] Cores
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Übergangsmetallkomplexe mit Schwefelliganden, CXXXIII [1]. Synthese, Struktur und Eigenschaften neuer FeII-Komplexe mit [FeN2S2]-Gerüsten / Transition Metal Complexes with Sulfur Ligands, CXXXIII [1]. Synthesis, Structure, and Properties of New FeII Complexes with [Fe2N2S2] Cores

  • Dieter Sellmann , Susanne Emig , Frank W. Heinemann and Falk Knoch
Published/Copyright: June 2, 2014
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Zeitschrift für Naturforschung B
From the journal Zeitschrift für Naturforschung B Volume 53 Issue 12

Abstract

In order to obtain suitable precursors for iron complexes that model the reactivity of the active sites of nitrogenases, the coordination chemistry of the [Fe(′N2H2S2′)] fragment was systematically investigated(′N2H2S2′2- = 1,2-ethanediamine-N,N′-bis(2-benzenethiolate)(2-)). One-pot reactions of FeCl2 -4H2O with the tetradentate amine-thiolate ligand ′N2H2S2′2- and CO, PR3 or P(OR)3 yielded the complexes [Fe(CO)2(′N2H2S2′)] (1), [Fe(CO)(PR3)(′N2H2S2′)] (R = Et (2), Pr (3), Bu (4)), [Fe(PMe3)2 (′N2H2S2′)] (7), [Fe(dppe)(′N2H2S2′)] (8 , dppe = 1,2- bis(diphenylphosphine)ethane), and [Fe(P(ÖR)3)2(′N2H2S2′)l (R = Me (9), Pr (10)). Mixed phosphane/phosphite complexes [Fe(PMe3)(P(OR)3)(′N2H2S2′)] (R = Me (11), Pr (12)) were synthesized by PMe3/P(OPr)3 exchange of the labile complexes [Fe(PMe3 )2(′N2H2S2′)] (7) and [Fe(P(OPr)3)2(′N2H2S2′)] (10). The [Fe(CO)(PR3)(′N2H2S2′)l complexes 3 and 4 also resulted from 1 and PR3 by photochemical CO substitution. They exhibit characteristic low-frequency v (CO) bands ( ≈1925 cm-1), and their remaining CO ligand proved photolytically inert. Reaction of 3 or 4 with NOBF4 yielded the dinuclear NO complex [Fe(NO)(′N2HS2′)]2 (6 ) which contains two amide functions.

Contrary to expectations, [Fe(PR3)2(′N2H2S2′)l complexes could not be obtained with monodentate phosphanes other than PMe3. The corresponding N-methylated ligand ′N2Me2S2,2- yielded only the complexes [Fe(CO)2 (′N2Me2S2′)] (15) and [Fe(′N2Me2S2′)] (16). X-ray structure analyses of complexes 7, 8 -MeOH, 3, [Fe(CO)(dppm)(′N2H2S2 ′)]·0,5 THF (5 ·0,5THF, dppm = bis(diphenylphosphino)methane), and 12·0,5′N2 H2S2 ′-H2 confirm the pseudo-octahedral coordination of the Fe centers by two trans-S and two cis-N donors and two c/s-coligands. The structural data further suggest that the unexpected instability of the [Fe(PR3)2 (′N1H2S2′)] complexes is not caused by steric but by electronic effects. The cyclic voltammograms and the reactivity of the [Fe(L)(L′)(′N2H2S2′)] complexes corroborate this assumption. The oxidation behaviour of the [Fe(L)(L′)(′N2H2S2′)] complexes depends critically on the coligands L and L′. Reaction of 1 with dioxygen leads to oxidative dehydrogenation of the ′N2H2S2′2- ligand and yields the dinuclear Schiff-Base complex [Fe(′gma′ )]2 (′gma′2- = glyoxal-bis(2- mercaptoanil)(2-)). In contrast, oxidation of [Fe(CO)(PR3)(′N2H2S2′)], [Fe(PR3)2 (′N2H2S2′)] and [Fe(P(OR)3)2 (′N2H2S2)] complexes by dioxygen occurs metal-centered and gives the Fe(IV) complexes [Fe(PR3)(′N2S2′)] (R = Me, Pr), [Fe(P(OR)3)(′N2S2′)] (R = Me) and [Fe(′N2S2′)]2 that contain the tetraanionic thiolate-amide ligand ′N2S2′4-.

Keywords: Iron Sulfur Complexes; Amine Ligands; Phosphane Ligands; X-Ray Data Cyclic Voltammetry
Received: 1998-7-9
Published Online: 2014-6-2
Published in Print: 1998-12-1

© 1946 – 2014: Verlag der Zeitschrift für Naturforschung

Articles in the same Issue

  1. Die Kristallstruktur von N,N'-Ditosyl-/7-phenylendiamin, Dichtefunktionaltheorie-Berechnungen von Konformationen und Wasserstoffbrücken-Motive von Sulfonamiden / Interactions in M olecular Crystals, 146 [1, 2], The Crystal Structure of N,N'-Ditosyl-p-phenylenediam ine, Density Functional Theory Calculations of Conformations and Hydrogen Bond Motifs in Sulfonamides
  2. Wechselwirkungen in Molekülkristallen, 147 [1, 2]. Isostrukturelle Wirt/Gast-Einschluß-Verbindungen von N,N'-Ditosyl- p-phenylendiamin mit Aceton, Cyclopentanon, Cyclopent-2-en-l-on, 1,3-Dioxolan, Tetrahydrofuran und 2,5-Dihydrofuran / Interactions in Molecular Crystals, 147 [1, 2], Isostructural Host/Guest-Inclusion Compounds of N,N'-Ditosyl-p-phenylenediamine with Acetone, Cyclopentanone, Cyclopent-2-ene-l-one, 1,3-Dioxolane, Tetrahydrofurane, and 2,5-D ihydrofurane
  3. Wechselwirkungen in Molekülkristallen, 148 [1,2 ]. Wirt/Gast-Einschlußverbindungen von N,N'-Ditosyl-p-phenylendiamin mit Furan, Benzol und Dioxan / Interactions in M olecular Crystals, 148 [1, 2]. Host/Guest-Inclusion Compounds of N ,N'-Ditosyl-p-phenylenediamine with Furane, Benzene and Dioxane
  4. Wechselwirkungen in Molekülkristallen, 149 [1 -3]. Wirt/Gast-Einschlußverbindungen von NjN'-Ditosyl-p-phenylendiamin: Die Wasserstoffbrücken-Addukte mit Morpholin; Pyridin, N,N-Dimethylformamid und Dimethylsulfoxid / Interactions in Molecular Crystals, 149 [1 - 3]. Host/Guest-Inclusion Compounds of N,N'-Ditosyl-/?-phenylenediamine: The Hydrogen Bonded Adducts with Morpholine, Pyridine, N ,N -Dimethylform amide, and Dimethylsulfoxide
  5. Oligomere Tetraeder-Anionen in Borophosphaten: Sechserringe mit offenen und cyclischen Phosphat-Verzweigungen in der Kristallstruktur von K6Cu2[B4P8O28(OH)6] / Oligomeric Tetrahedral Anions in Borophosphates: Six-Membered Rings with Open and Cyclic Phosphate Branchings in the Crystal Structure of K6Cu2[B4P8O28(OH)6]
  6. Four Novel N3O4 Donor Macrocycles and their Lanthanide(III) Complexes
  7. Reaktionen des donorfreien (CF3)2Cd mit Phosphor(V)halogeniden: Difluorcarben-Einschiebungen und Direktsynthese von (CF3)3PF2 / Reactions of Donor-Free (CF3)2Cd with Phosphorus(V) Halides: Insertion of Difluorocarbene and Direct Synthesis of (CF3)3PF2
  8. Übergangsmetallkomplexe mit Schwefelliganden, CXXXIII [1]. Synthese, Struktur und Eigenschaften neuer FeII-Komplexe mit [FeN2S2]-Gerüsten / Transition Metal Complexes with Sulfur Ligands, CXXXIII [1]. Synthesis, Structure, and Properties of New FeII Complexes with [Fe2N2S2] Cores
  9. Arsenic(III), Antimony (III) and Bismuth(III) Thiobenzoates: Crystal and Molecular Structures of M(SOCR)3 and PhSb(SOCPh)2
  10. BaCu6Ge2S8 -Ein Thiogermanat als Variante der Li3Bi-Struktur / BaCu6Ge2S8 -A Thiogermanate as a Variant of the Li3Bi Structure
  11. Tetrazinn(II)-und Bariumtrizinn(II)-tetrakis[μ3 -tri-ter/-butyIsilylphosphan- diid]-Verbindungen mit einem Tetrametallatetraphosphacuban-Gerüst / Tetratin(II) and Barium Tritin(II) Tetrakis[μ3-tri-rm-butylsilylphosphandiide] Compounds with a Tetrametallatetraphosphacubane Core
  12. Determination of Coupling Signs 1J(119Sn, 15N ) and 2J(119Sn, 117Sn) in Trimethylstannylamines
  13. Metallkomplexe mit biologisch wichtigen Liganden, CIX [1]. Metallorganische Verbindungen von Platin(II), Ruthenium(II), Rhodium (III) und Iridium (III) mit Oxocarbonyl-N-geschützten a-Am inosäuren und L-Methionylglycinat / Metal Complexes with Biologically Important Ligands, CIX [1]. Organometallic Compounds of Platinum(II), Ruthenium(II), Rhodium(III), and Iridium(III) with Oxocarbonyl-N-protected a-Amino Acids and L-Methionylglycinate
  14. Phosphenium-Komplexe, XXIX [1]. [4+2]-Cycloadditionen von Phospheniumkomplexen des Typs Cp(OC)2W = PR2(R = Alkyl, Aryl) mit 2,3-Dimethylbutadien / Phosphenium Complexes, XXIX [1], [4+2]-Cycloaddition of Phosphenium Complexes of the Type Cp(OC)2W=PR2 (R = Alkyl, Aryl) with 2,3-Dimethylbutadiene
  15. Molecular Recognition Analyzed by Observing Intramolecular Interconversion with EPR Spectroscopy
  16. Synthesis of the Stereoisomers of β-Hydroxyhistidine and their Analytical Identification in Hydrolysates of Bacterial Peptides
  17. The Structure of Lithiumiodide 3-Tetrahydrofuran
  18. Benzo-18-krone-6 -Acetonitril (1/2): Kristallisation und Tieftemperatur- Röntgenstrukturanalyse / Benzo-18 -crown-6 -Acetonitrile (1/2): Crystallization and Low-Temperature X-Ray Analysis
  19. Subject Index
  20. Authors Index
https://doi.org/10.1515/znb-1998-1208
Keywords for this article
Iron Sulfur Complexes; Amine Ligands; Phosphane Ligands; X-Ray Data Cyclic Voltammetry

Articles in the same Issue

  1. Die Kristallstruktur von N,N'-Ditosyl-/7-phenylendiamin, Dichtefunktionaltheorie-Berechnungen von Konformationen und Wasserstoffbrücken-Motive von Sulfonamiden / Interactions in M olecular Crystals, 146 [1, 2], The Crystal Structure of N,N'-Ditosyl-p-phenylenediam ine, Density Functional Theory Calculations of Conformations and Hydrogen Bond Motifs in Sulfonamides
  2. Wechselwirkungen in Molekülkristallen, 147 [1, 2]. Isostrukturelle Wirt/Gast-Einschluß-Verbindungen von N,N'-Ditosyl- p-phenylendiamin mit Aceton, Cyclopentanon, Cyclopent-2-en-l-on, 1,3-Dioxolan, Tetrahydrofuran und 2,5-Dihydrofuran / Interactions in Molecular Crystals, 147 [1, 2], Isostructural Host/Guest-Inclusion Compounds of N,N'-Ditosyl-p-phenylenediamine with Acetone, Cyclopentanone, Cyclopent-2-ene-l-one, 1,3-Dioxolane, Tetrahydrofurane, and 2,5-D ihydrofurane
  3. Wechselwirkungen in Molekülkristallen, 148 [1,2 ]. Wirt/Gast-Einschlußverbindungen von N,N'-Ditosyl-p-phenylendiamin mit Furan, Benzol und Dioxan / Interactions in M olecular Crystals, 148 [1, 2]. Host/Guest-Inclusion Compounds of N ,N'-Ditosyl-p-phenylenediamine with Furane, Benzene and Dioxane
  4. Wechselwirkungen in Molekülkristallen, 149 [1 -3]. Wirt/Gast-Einschlußverbindungen von NjN'-Ditosyl-p-phenylendiamin: Die Wasserstoffbrücken-Addukte mit Morpholin; Pyridin, N,N-Dimethylformamid und Dimethylsulfoxid / Interactions in Molecular Crystals, 149 [1 - 3]. Host/Guest-Inclusion Compounds of N,N'-Ditosyl-/?-phenylenediamine: The Hydrogen Bonded Adducts with Morpholine, Pyridine, N ,N -Dimethylform amide, and Dimethylsulfoxide
  5. Oligomere Tetraeder-Anionen in Borophosphaten: Sechserringe mit offenen und cyclischen Phosphat-Verzweigungen in der Kristallstruktur von K6Cu2[B4P8O28(OH)6] / Oligomeric Tetrahedral Anions in Borophosphates: Six-Membered Rings with Open and Cyclic Phosphate Branchings in the Crystal Structure of K6Cu2[B4P8O28(OH)6]
  6. Four Novel N3O4 Donor Macrocycles and their Lanthanide(III) Complexes
  7. Reaktionen des donorfreien (CF3)2Cd mit Phosphor(V)halogeniden: Difluorcarben-Einschiebungen und Direktsynthese von (CF3)3PF2 / Reactions of Donor-Free (CF3)2Cd with Phosphorus(V) Halides: Insertion of Difluorocarbene and Direct Synthesis of (CF3)3PF2
  8. Übergangsmetallkomplexe mit Schwefelliganden, CXXXIII [1]. Synthese, Struktur und Eigenschaften neuer FeII-Komplexe mit [FeN2S2]-Gerüsten / Transition Metal Complexes with Sulfur Ligands, CXXXIII [1]. Synthesis, Structure, and Properties of New FeII Complexes with [Fe2N2S2] Cores
  9. Arsenic(III), Antimony (III) and Bismuth(III) Thiobenzoates: Crystal and Molecular Structures of M(SOCR)3 and PhSb(SOCPh)2
  10. BaCu6Ge2S8 -Ein Thiogermanat als Variante der Li3Bi-Struktur / BaCu6Ge2S8 -A Thiogermanate as a Variant of the Li3Bi Structure
  11. Tetrazinn(II)-und Bariumtrizinn(II)-tetrakis[μ3 -tri-ter/-butyIsilylphosphan- diid]-Verbindungen mit einem Tetrametallatetraphosphacuban-Gerüst / Tetratin(II) and Barium Tritin(II) Tetrakis[μ3-tri-rm-butylsilylphosphandiide] Compounds with a Tetrametallatetraphosphacubane Core
  12. Determination of Coupling Signs 1J(119Sn, 15N ) and 2J(119Sn, 117Sn) in Trimethylstannylamines
  13. Metallkomplexe mit biologisch wichtigen Liganden, CIX [1]. Metallorganische Verbindungen von Platin(II), Ruthenium(II), Rhodium (III) und Iridium (III) mit Oxocarbonyl-N-geschützten a-Am inosäuren und L-Methionylglycinat / Metal Complexes with Biologically Important Ligands, CIX [1]. Organometallic Compounds of Platinum(II), Ruthenium(II), Rhodium(III), and Iridium(III) with Oxocarbonyl-N-protected a-Amino Acids and L-Methionylglycinate
  14. Phosphenium-Komplexe, XXIX [1]. [4+2]-Cycloadditionen von Phospheniumkomplexen des Typs Cp(OC)2W = PR2(R = Alkyl, Aryl) mit 2,3-Dimethylbutadien / Phosphenium Complexes, XXIX [1], [4+2]-Cycloaddition of Phosphenium Complexes of the Type Cp(OC)2W=PR2 (R = Alkyl, Aryl) with 2,3-Dimethylbutadiene
  15. Molecular Recognition Analyzed by Observing Intramolecular Interconversion with EPR Spectroscopy
  16. Synthesis of the Stereoisomers of β-Hydroxyhistidine and their Analytical Identification in Hydrolysates of Bacterial Peptides
  17. The Structure of Lithiumiodide 3-Tetrahydrofuran
  18. Benzo-18-krone-6 -Acetonitril (1/2): Kristallisation und Tieftemperatur- Röntgenstrukturanalyse / Benzo-18 -crown-6 -Acetonitrile (1/2): Crystallization and Low-Temperature X-Ray Analysis
  19. Subject Index
  20. Authors Index
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