Carbonylmetall‐Komplexe mit Ferrocendithiocarboxylato‐Liganden

Herberhold, Max; Ott, J.; Haumaier, Ludwig

doi:10.1002/cber.19851180813

Cited by 21 publications

(3 citation statements)

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“…This result suggests that the presence of the CS 2 group on the ligand FcCS 2 favors the oxidation of the Fe(II) atom by the precursor technetium complex, a fact that is probably related to the existence of the resonance forms depicted in Figure . Specifically, in form II, the electronic density is driven toward the CS 2 group and the Fe atom becomes more positive 3 Resonance forms for the monoanionic ligand FeCS 2 . …”

Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of Nitrido Tc(V) and Re(V) Complexes with Ferrocenedithiocarboxylate {FcCS₂ = [Fe(C₅H₄CS₂)(C₅H₅)]^-}

et al. 1997

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The first mixed technetium-iron complexes [(99g)Tc(N)(FcCS(2))(2)] {FcCS(2) = [Fe(II)(C(5)H(5))(C(5)H(4)CS(2))](-)} (1) and [(99g)Tc(N)(FcCS(2))(FcCS(2)( bigstar))](+) {FcCS(2) = [Fe(II)(C(5)H(5))(C(5)H(4)CS(2))](-); FcCS(2)( bigstar) = Fe(III)(C(5)H(5))(C(5)H(4)CS(2))} (2) have been prepared and characterized. Complex 1 was obtained by reaction of the precursor complex [(99g)Tc(N)Cl(2)(PPh(3))(2)] with the piperidinium salt of the ligand FcCS(2). The resulting biferrocene complex is formed by two FcCS(2) ligands bound to the Tc atom through the four sulfur atoms of the two CS(2)(-) groups and bridged by a Tc&tbd1;N multiple bond. The mixed-valence Fe(2+)-Fe(3+), monocationic complex 2 was isolated as secondary product of the reaction of the precursor complex [(99g)Tc(N)Cl(4)](-) with the ligand FcCS(2). It has the same composition as 1 except for the fact that the Fe(II) center of one FcCS(2) ligand has been oxidized to Fe(III). The electrochemical properties of 1 and 2 are consistent with their formulations. Cyclic voltammetric studies and controlled potential electrolyses showed that complex 1 undergoes a quasi-reversible, two-electron exchange at 0.320 V (vs ferrocene/ferrocenium couple) attributed to the oxidation of the two Fe(II) ions, while complex 2 undergoes a quasi-reversible, one-electron exchange at nearly the same potential (0.344 V) assigned to the oxidation of the residual Fe(II) ion. These results indicate that in complex 1 the two Fe(II) atoms behave as independent redox centers. The synthesis, characterization, and electrochemical behavior of the analogous, six-coordinated rhenium(V) complex [Re(N)(FcCS(2))(2)(PPh(3))] are also reported.

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Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of Nitrido Tc(V) and Re(V) Complexes with Ferrocenedithiocarboxylate {FcCS₂ = [Fe(C₅H₄CS₂)(C₅H₅)]^-}

et al. 1997

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“…Although ferrocene dithiocarboxylate has been known as a ligand since 1974, it has been rarely used in coordination chemistry. Although some metal salts, as well as cyclopentadienyl, nitrido, and carbonyl complexes of ferrocene dithiocarboxylate have been reported, to the best of our knowledge no structurally characterized derivative and no gold complex is known. Thus, ferrocene dithiocarboxylate has been neglected as ligand.…”

Section: Introductionmentioning

confidence: 98%

High-Coordinate Gold(I) Complexes with Dithiocarboxylate Ligands

et al. 2014

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Ferrocene dithiocarboxylate has been introduced into the chemistry of gold(I) and copper(I). First, a modified synthesis of piperidinium ferrocene dithiocarboxylate (1) is reported. Reaction of this reagent with [Au(tht)Cl] in the presence of different phosphines resulted in monomeric, dimeric, and polymeric structures. Although gold(I) is usually two coordinate, mainly three- and four-fold coordinated compounds were obtained by using ferrocene dithiocarboxylate as ligands. The isolated compounds are [(FcCSS)Au(PPh3)2] (2) (FcCSS = ferrocene dithiocarboxylate), [(FcCSS)Au2(dppm)2] (3) (dppm = bis(diphenylphosphino)methane), and [(FcCSS)Au(dppf)]n (4) (dppf = bis(diphenylphosphino)ferrocene) [{(FcCSS)Au}2(dppp)] (5) (dppp = bis(diphenylphosphino)propane). The FcCSS ligand shows a remarkable flexible coordination mode. It coordinates either in a monodentate, a chelating, or in a metal bridging mode. In the four gold(I) complexes 2-5 four different coordination modes of the FcCSS ligand are seen. Attempts to extend this rich coordination chemistry to other coinage metals were only partly successful. [(FcCSS)Cu(PPh3)2] (6) was obtained from the reaction of piperidinium ferrocene dithiocarboxylate with [(Ph3P)3CuCl]. (57)Fe-Mössbauer spectroscopy was performed for compounds 2-4. The spectra show isomer shifts and quadrupole splittings that are typical for diamagnetic ferrocenes.

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“…'1070 Compounds of the type [M(CO) 2 (E 2 CR)Cp] can also be made by insertion of sulfur (or selenium) into the carbyne complexes [M(CO) 2 (sCR)Cp] 1071 '1072 and by reaction of RCS 2 " with [M(CO) 3 (L)Cp] + (L = solvent) 238. …”

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Cyclopentadienyl Complexes of Chromium, Molybdenum and Tungsten

Morris

1995

Comprehensive Organometallic Chemistry II

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Carbonylmetall‐Komplexe mit Ferrocendithiocarboxylato‐Liganden

Abstract: Carbonylmetal Complexes with Ferrocendithiocarboxylato Ligands Reaction of the carbonylmetal cations

Cited by 21 publications

References 15 publications

Synthesis and Characterization of Nitrido Tc(V) and Re(V) Complexes with Ferrocenedithiocarboxylate {FcCS₂ = [Fe(C₅H₄CS₂)(C₅H₅)]^-}

Synthesis and Characterization of Nitrido Tc(V) and Re(V) Complexes with Ferrocenedithiocarboxylate {FcCS₂ = [Fe(C₅H₄CS₂)(C₅H₅)]^-}

High-Coordinate Gold(I) Complexes with Dithiocarboxylate Ligands

Cyclopentadienyl Complexes of Chromium, Molybdenum and Tungsten

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Carbonylmetall‐Komplexe mit Ferrocendithiocarboxylato‐Liganden

Abstract: Carbonylmetal Complexes with Ferrocendithiocarboxylato Ligands Reaction of the carbonylmetal cations

Cited by 21 publications

References 15 publications

Synthesis and Characterization of Nitrido Tc(V) and Re(V) Complexes with Ferrocenedithiocarboxylate {FcCS2 = [Fe(C5H4CS2)(C5H5)]-}

Synthesis and Characterization of Nitrido Tc(V) and Re(V) Complexes with Ferrocenedithiocarboxylate {FcCS2 = [Fe(C5H4CS2)(C5H5)]-}

High-Coordinate Gold(I) Complexes with Dithiocarboxylate Ligands

Cyclopentadienyl Complexes of Chromium, Molybdenum and Tungsten

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Synthesis and Characterization of Nitrido Tc(V) and Re(V) Complexes with Ferrocenedithiocarboxylate {FcCS₂ = [Fe(C₅H₄CS₂)(C₅H₅)]^-}

Synthesis and Characterization of Nitrido Tc(V) and Re(V) Complexes with Ferrocenedithiocarboxylate {FcCS₂ = [Fe(C₅H₄CS₂)(C₅H₅)]^-}