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ESEEM and Mössbauer studies of the ferriheme model compound bis(3-aminopyrazole)tetraphenylporphyrinatoiron(III) chloride, [TPPFe(NH2PzH)2]Cl (1999)

Schünemann, Volker ; Raitsimring, Arnold M. ; Benda, Rüdiger ; [et al.]

Springer

JBIC 4 (1999), S. 708-716

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ISSN: 1432-1327

Keywords: Key words g-Tensor determination of ferriheme model compound ; Electron spin echo envelope modulation spectroscopy ; Mössbauer spectroscopy ; Electron paramagnetic resonance spectroscopy ; Electronic ground state

Source: Springer Online Journal Archives 1860-2000

Topics: Biology , Chemistry and Pharmacology

Notes: Abstract A model heme complex, bis(3-aminopyrazole)tetraphenylporphinatoiron(III) chloride, [TPPFe (NH2PzH)2]Cl, for which the EPR g-values lead to a rhombicity V/Δ=1.2 if g zz is the largest g-value, have been investigated by electron spin echo envelope modulation (ESEEM) and Mössbauer spectroscopies. The ESEEM studies focus on the proton sum frequency peaks at near twice the proton Larmor frequency. Analysis of the distant proton peak (mainly due to the pyrrole-H) at exactly twice the proton Larmor frequency shows conclusively that g zz is aligned along the normal to the porphyrin plane, and thus the electron configuration is (d xy )2(d xz ,d yz )3, with g zz 〉g yy 〉g xx . This system is thus another violation to Taylor's "proper axis system" rule. The near proton (the α-H and N-H of the axial ligands) peaks provide distance information for those protons from the metal. Magnetic Mössbauer studies of the same complex confirm the (d xy )2(d xz ,d yz )3 ground state and indicate that, as is the case for cytochrome P450cam, A xx is the largest magnitude A-value, and is negative in sign. Other low-spin iron(III) porphyrinates also have A xx of negative sign, but usually the magnitude is only about half that of A zz , which is always positive in sign.

Type of Medium: Electronic Resource

URL: http://dx.doi.org/10.1007/s007750050343

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Darstellung von Metall-Schwefel-Clustern durch einfache Reaktion von Metallsalzen mit H2S: R2(NH4)[Cu3S12], R2[Cu4S12] · CH3CN, R2[Cu4S12,8], R2[Fe2S2(S5)2], R2[Fe4S4Br4], R2[Fe4S4Br2Cl2], R2[Fe4S4Cl4], R2[Fe2S2Cl4] (R = PPh4) und [Fe(DMF)6][Fe2S2Cl4]Professor Friedo Huber zum 60. Geburtstage am 4. Juni 1989 gewidmet (1989)

Müller, A. ; Schladerbeck, N. H. ; Krickemeyer, E. ; [et al.]

Weinheim : Wiley-Blackwell

Zeitschrift für anorganische Chemie 570 (1989), S. 7-36

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ISSN: 0044-2313

Keywords: Chemistry ; Inorganic Chemistry

Source: Wiley InterScience Backfile Collection 1832-2000

Topics: Chemistry and Pharmacology

Description / Table of Contents: Preparation of Metal-Sulfur-Clusters by Simple Reaction of Metal-Salts with H2S: R2(NH4) [Cu3S12], R2[Cu4S12] · CH3CN, R2[Cu4S12,8], R2[Fe2S2(S5)2], R2[Fe4S4Br4], R2[Fe4S4Br2Cl2], R2[Fe4S4Cl4], R2[Fe2S2Cl4] (R = PPh4) and [Fe(DMF)6][Fe2S2Cl4]Simple preparation methods for metal sulfur clusters from simple metal salts and H2S in solution are reported (for the systems Cum+/H2S and Fen+/H2S). The compounds R2(NH4)[Cu3S12], R2[Cu4S12] · CH3CN, R2[Cu4S12,8], R2[Fe2S2(S5)2], R2[Fe4S4Br4], R2[Fe4S4Br2Cl2], R2[Fe4S4Cl4], R2[Fe2S2Cl4] (R = PPh4) and [Fe(DMF)6][Fe2S2Cl4] were characterized spectroscopically (IR, Raman, Fe-Mössbauer) and by complete crystal structure analyses (except R2[Fe2S2(S5)2] and R2[Fe2S2Cl4]).For structural data see Inhaltsübersicht.

Notes: Es wird über eine einfache Darstellungsmöglichkeit von Metall-Schwefel-Clustern aus einfachen Metall-Salzen und H2S in Lösung berichtet und zwar für die Systeme Cum+/H2S und Fen+/H2S. Die Verbindungen R2(NH4)[Cu3S12], R2[Cu4S12] · CH3CN, R2[Cu4S12,8], R2[Fe2S2(S5)2], R2[Fe4S4Br4], R2[Fe4S4Br2Cl2], R2[Fe4S4Cl4], R2[Fe2S2Cl4] (R = PPh4) und [Fe(DMF)6][Fe2S2Cl4] wurden spektroskopisch (IR, Raman, Fe-Mößbauer) sowie durch vollständige Kristallstrukturanalyse charakterisiert (mit Ausnahme von R2[Fe2S2(S5)2]).(PPh4)2(NH4)[Cu4S12]: P1, a = 1266,0(5), b = 1 489,6(6), c = 1 493,6(6) pm, α = 74,72(3), β = 86,40(3), γ = 77,52(3)°, V = 2 652,9 · 106 pm3, Z = 2; R = 0,057 für 8377 unabhängige Reflexe (Fo 〉 3,92 σ(Fo)).(PPh4)2(NH4)[Cu4S12] · CH3CN: P1, a = 1 062,2(3), b = 1 336,2(4), c = 2 137,8(6) pm, α = 102,42(2), β = 90,60(2), γ = 110,16(2)°, V = 2 769,8 · 106 pm3, Z = 2; R = 0,076 für 4312 unabhängige Reflexe (Fo 〉 3,92 σ(Fo)).(PPh4)2[Cu4S12,8]: P21/n, a = 1 245,2(8), b = 1 306,9(10), c = 3348,7(22) pm, β = 98,90(5°), V = 5383,9 · 106 pm3, Z = 4; R = 0,094 für 4814 unabhängige Reflexe (Fo 〉 3,92 σ(Fo)).(PPh4)2[Fe4S4Br4]: C2/c, a = 1585,8(6), b = 1440,6(4), c = 2419,7(9) pm, β = 112,74(3)°, V = 5 098,1 · 106 pm3, Z = 4; R = 0,068 für 3 247 unabhängige Reflexe (Fo 〉 3,92 σ(Fo)).(PPh4)2[Fe4S4Br2Cl2]: C2/c, a = 1592,3(3), b = 1432,9(3), c = 2325,0(5) pm, β = 106,43(2)°, V = 5 088,1 · 106 pm3, Z = 4; R = 0,084 für 1982 unabhängige Reflexe (Fo 〉 3,92 σ(Fo)).(PPh4)2[Fe4S4Cl4]: C2/c, a = 1593,9(3), b = 1420,8(2), c = 2316,9(4) pm, β = 106,65(1)°, V = 5026,9 · 106 pm3, Z = 4; R = 0,069 für 3 902 unabhängige Reflexe (Fo 〉 3,92 σ(Fo)).[Fe(DMF)6][Fe2S2Cl4]: P1, a = 923,5(4), b = 941,4(4), c = 1123,9(5) pm, α = 75,29(4), β = 71,17(3), γ = 87,27(4)°, V = 893,9 · 106 pm3, Z = 1; R = 0,067 für 1832 unabhängige Reflexe (Fo 〉 3,92 σ(Fo)).

Additional Material: 11 Ill.