Structure, Stability, and Redox Properties of MnII, FeII, CoII, and CoIII Complexes with 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol

Michele Ghisletta, Lorenza Hausherr-Primo, K. Gajda-Schrantz, Gábor Machula, László Nagy, Helmut W. Schmalle, Greti Rihs, Frank Endres, Kaspar Hegetschweiler

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Abstract

The interaction of MnII, FeII, and CoII with the ligand taci (=1,3,5-triamino-1,3,5-trideoxy-cis-inositol) was studied in the solid state and in aqueous solution. Magnetic susceptibility measurements revealed a high-spin electron configuration for the Mn and the Fe complexes. Crystal data: [Mn(taci)2](NO3)2·2H2O (1), C12H34MnN3O14, monoclinic, space group P21/c, a = 7.107(5) Å, b = 8.742(2) Å, c = 18.527(6) Å, β= 100.20(4)°, Z = 2; [Fe(taci)2]Cl2·6H2O (2), C12Cl2FeH42N6O12, monoclinic, space group C2/m, a = 11.420(2) Å, b = 9.300(2) Å, c = 13.330(3) Å, β = 111.97(3)°, Z = 2; [Co(taci)2](NO3)2·1.5H2O (3), C12CoH33N8O13.5, monoclinic, space group P21/c, a = 7.081(1) Å, b = 8.743(1) Å, c = 18.181(2) Å, β= 99.49(1)°, Z = 2. All three structures exhibited distorted octahedral MN6 coordination. The stability constants for the complexes [M(taci)]2+ (M = Mn, Fe, Co) and [M(taci)2]2+ (M = Fe, Co) in aqueous media have been evaluated by potentiometric titration. Comparison with other divalent cations showed that the order of stability increases MnII <CdII ≈ FeII <ZnII <CoII <CuII <NiII. In alkaline aqueous media, the complexes 1-3 are readily oxidized by dioxygen. The redox properties were analyzed by a series of polarographic and cyclic voltammetric measurements. A new isomeric form of a bis-taci CoIII complex was formed, where one of the taci ligands coordinates the metal cation by one nitrogen and two oxygen atoms. The complex was isolated in crystalline form as [Co(taci)(Htaci)](NO3)4·0.5H2O (4), C12-CoH32N32O18O18.5, monoclinic, space group C2/c, a = 30.541(3) A, b = 9.015(1) Å, c = 17.852(2) Å, β= 95.63(1)°, Z = 8. [Co(tach)(H2O)x(NO3)3-x] x+ (tach = all-cis-1,3,5-triaminocyclohexane, 0 ≤ x ≤ 3) was used as a model to demonstrate that, for CoIII, the substitution of the three monodentate coligands by a taci molecule resulted generally in an asymmetric binding. An N,O,O and an N,N,O coordination mode were observed for [Co(taci)(tach)](NO3)3·3H2O (5), and [Co(H-itaci)(tach)](NO3)2·(3 - x)H2O·MeOH, 0.2 ≤ x ≤ 0.5 (6), respectively. Crystal data: 5 (C12CoH36N9O15), monoclinic, P21/n, a = 8.942(5) Å, b = 30.07(3) Å, c = 9.354(5) Å, β= 109.25(4)°, Z = 4; 6 (x ≈ 0.2, C12CoH12.2N8O12), monoclinic, P21/n, a = 7.337(2) Å, b = 19.847(4) Å, c = 15.226(3) Å, β= 93.59(3)°, Z = 4.

Original languageEnglish
Pages (from-to)997-1008
Number of pages12
JournalInorganic Chemistry
Volume37
Issue number5
Publication statusPublished - 1998

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inositols
Inositol
Oxygen
Ligands
Crystals
Divalent Cations
Magnetic susceptibility
Titration
Cations
Substitution reactions
Nitrogen
Metals
Crystalline materials
cations
Atoms
ligands
Molecules
Electrons
titration
electron spin

ASJC Scopus subject areas

  • Inorganic Chemistry

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Ghisletta, M., Hausherr-Primo, L., Gajda-Schrantz, K., Machula, G., Nagy, L., Schmalle, H. W., ... Hegetschweiler, K. (1998). Structure, Stability, and Redox Properties of MnII, FeII, CoII, and CoIII Complexes with 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol. Inorganic Chemistry, 37(5), 997-1008.

Structure, Stability, and Redox Properties of MnII, FeII, CoII, and CoIII Complexes with 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol. / Ghisletta, Michele; Hausherr-Primo, Lorenza; Gajda-Schrantz, K.; Machula, Gábor; Nagy, László; Schmalle, Helmut W.; Rihs, Greti; Endres, Frank; Hegetschweiler, Kaspar.

In: Inorganic Chemistry, Vol. 37, No. 5, 1998, p. 997-1008.

Research output: Contribution to journalArticle

Ghisletta, M, Hausherr-Primo, L, Gajda-Schrantz, K, Machula, G, Nagy, L, Schmalle, HW, Rihs, G, Endres, F & Hegetschweiler, K 1998, 'Structure, Stability, and Redox Properties of MnII, FeII, CoII, and CoIII Complexes with 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol', Inorganic Chemistry, vol. 37, no. 5, pp. 997-1008.
Ghisletta, Michele ; Hausherr-Primo, Lorenza ; Gajda-Schrantz, K. ; Machula, Gábor ; Nagy, László ; Schmalle, Helmut W. ; Rihs, Greti ; Endres, Frank ; Hegetschweiler, Kaspar. / Structure, Stability, and Redox Properties of MnII, FeII, CoII, and CoIII Complexes with 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol. In: Inorganic Chemistry. 1998 ; Vol. 37, No. 5. pp. 997-1008.
@article{b396d4918c064b0bbf8f74c9bac6ff93,
title = "Structure, Stability, and Redox Properties of MnII, FeII, CoII, and CoIII Complexes with 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol",
abstract = "The interaction of MnII, FeII, and CoII with the ligand taci (=1,3,5-triamino-1,3,5-trideoxy-cis-inositol) was studied in the solid state and in aqueous solution. Magnetic susceptibility measurements revealed a high-spin electron configuration for the Mn and the Fe complexes. Crystal data: [Mn(taci)2](NO3)2·2H2O (1), C12H34MnN3O14, monoclinic, space group P21/c, a = 7.107(5) {\AA}, b = 8.742(2) {\AA}, c = 18.527(6) {\AA}, β= 100.20(4)°, Z = 2; [Fe(taci)2]Cl2·6H2O (2), C12Cl2FeH42N6O12, monoclinic, space group C2/m, a = 11.420(2) {\AA}, b = 9.300(2) {\AA}, c = 13.330(3) {\AA}, β = 111.97(3)°, Z = 2; [Co(taci)2](NO3)2·1.5H2O (3), C12CoH33N8O13.5, monoclinic, space group P21/c, a = 7.081(1) {\AA}, b = 8.743(1) {\AA}, c = 18.181(2) {\AA}, β= 99.49(1)°, Z = 2. All three structures exhibited distorted octahedral MN6 coordination. The stability constants for the complexes [M(taci)]2+ (M = Mn, Fe, Co) and [M(taci)2]2+ (M = Fe, Co) in aqueous media have been evaluated by potentiometric titration. Comparison with other divalent cations showed that the order of stability increases MnII <CdII ≈ FeII <ZnII <CoII <CuII <NiII. In alkaline aqueous media, the complexes 1-3 are readily oxidized by dioxygen. The redox properties were analyzed by a series of polarographic and cyclic voltammetric measurements. A new isomeric form of a bis-taci CoIII complex was formed, where one of the taci ligands coordinates the metal cation by one nitrogen and two oxygen atoms. The complex was isolated in crystalline form as [Co(taci)(Htaci)](NO3)4·0.5H2O (4), C12-CoH32N32O18O18.5, monoclinic, space group C2/c, a = 30.541(3) A, b = 9.015(1) {\AA}, c = 17.852(2) {\AA}, β= 95.63(1)°, Z = 8. [Co(tach)(H2O)x(NO3)3-x] x+ (tach = all-cis-1,3,5-triaminocyclohexane, 0 ≤ x ≤ 3) was used as a model to demonstrate that, for CoIII, the substitution of the three monodentate coligands by a taci molecule resulted generally in an asymmetric binding. An N,O,O and an N,N,O coordination mode were observed for [Co(taci)(tach)](NO3)3·3H2O (5), and [Co(H-itaci)(tach)](NO3)2·(3 - x)H2O·MeOH, 0.2 ≤ x ≤ 0.5 (6), respectively. Crystal data: 5 (C12CoH36N9O15), monoclinic, P21/n, a = 8.942(5) {\AA}, b = 30.07(3) {\AA}, c = 9.354(5) {\AA}, β= 109.25(4)°, Z = 4; 6 (x ≈ 0.2, C12CoH12.2N8O12), monoclinic, P21/n, a = 7.337(2) {\AA}, b = 19.847(4) {\AA}, c = 15.226(3) {\AA}, β= 93.59(3)°, Z = 4.",
author = "Michele Ghisletta and Lorenza Hausherr-Primo and K. Gajda-Schrantz and G{\'a}bor Machula and L{\'a}szl{\'o} Nagy and Schmalle, {Helmut W.} and Greti Rihs and Frank Endres and Kaspar Hegetschweiler",
year = "1998",
language = "English",
volume = "37",
pages = "997--1008",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
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TY - JOUR

T1 - Structure, Stability, and Redox Properties of MnII, FeII, CoII, and CoIII Complexes with 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol

AU - Ghisletta, Michele

AU - Hausherr-Primo, Lorenza

AU - Gajda-Schrantz, K.

AU - Machula, Gábor

AU - Nagy, László

AU - Schmalle, Helmut W.

AU - Rihs, Greti

AU - Endres, Frank

AU - Hegetschweiler, Kaspar

PY - 1998

Y1 - 1998

N2 - The interaction of MnII, FeII, and CoII with the ligand taci (=1,3,5-triamino-1,3,5-trideoxy-cis-inositol) was studied in the solid state and in aqueous solution. Magnetic susceptibility measurements revealed a high-spin electron configuration for the Mn and the Fe complexes. Crystal data: [Mn(taci)2](NO3)2·2H2O (1), C12H34MnN3O14, monoclinic, space group P21/c, a = 7.107(5) Å, b = 8.742(2) Å, c = 18.527(6) Å, β= 100.20(4)°, Z = 2; [Fe(taci)2]Cl2·6H2O (2), C12Cl2FeH42N6O12, monoclinic, space group C2/m, a = 11.420(2) Å, b = 9.300(2) Å, c = 13.330(3) Å, β = 111.97(3)°, Z = 2; [Co(taci)2](NO3)2·1.5H2O (3), C12CoH33N8O13.5, monoclinic, space group P21/c, a = 7.081(1) Å, b = 8.743(1) Å, c = 18.181(2) Å, β= 99.49(1)°, Z = 2. All three structures exhibited distorted octahedral MN6 coordination. The stability constants for the complexes [M(taci)]2+ (M = Mn, Fe, Co) and [M(taci)2]2+ (M = Fe, Co) in aqueous media have been evaluated by potentiometric titration. Comparison with other divalent cations showed that the order of stability increases MnII <CdII ≈ FeII <ZnII <CoII <CuII <NiII. In alkaline aqueous media, the complexes 1-3 are readily oxidized by dioxygen. The redox properties were analyzed by a series of polarographic and cyclic voltammetric measurements. A new isomeric form of a bis-taci CoIII complex was formed, where one of the taci ligands coordinates the metal cation by one nitrogen and two oxygen atoms. The complex was isolated in crystalline form as [Co(taci)(Htaci)](NO3)4·0.5H2O (4), C12-CoH32N32O18O18.5, monoclinic, space group C2/c, a = 30.541(3) A, b = 9.015(1) Å, c = 17.852(2) Å, β= 95.63(1)°, Z = 8. [Co(tach)(H2O)x(NO3)3-x] x+ (tach = all-cis-1,3,5-triaminocyclohexane, 0 ≤ x ≤ 3) was used as a model to demonstrate that, for CoIII, the substitution of the three monodentate coligands by a taci molecule resulted generally in an asymmetric binding. An N,O,O and an N,N,O coordination mode were observed for [Co(taci)(tach)](NO3)3·3H2O (5), and [Co(H-itaci)(tach)](NO3)2·(3 - x)H2O·MeOH, 0.2 ≤ x ≤ 0.5 (6), respectively. Crystal data: 5 (C12CoH36N9O15), monoclinic, P21/n, a = 8.942(5) Å, b = 30.07(3) Å, c = 9.354(5) Å, β= 109.25(4)°, Z = 4; 6 (x ≈ 0.2, C12CoH12.2N8O12), monoclinic, P21/n, a = 7.337(2) Å, b = 19.847(4) Å, c = 15.226(3) Å, β= 93.59(3)°, Z = 4.

AB - The interaction of MnII, FeII, and CoII with the ligand taci (=1,3,5-triamino-1,3,5-trideoxy-cis-inositol) was studied in the solid state and in aqueous solution. Magnetic susceptibility measurements revealed a high-spin electron configuration for the Mn and the Fe complexes. Crystal data: [Mn(taci)2](NO3)2·2H2O (1), C12H34MnN3O14, monoclinic, space group P21/c, a = 7.107(5) Å, b = 8.742(2) Å, c = 18.527(6) Å, β= 100.20(4)°, Z = 2; [Fe(taci)2]Cl2·6H2O (2), C12Cl2FeH42N6O12, monoclinic, space group C2/m, a = 11.420(2) Å, b = 9.300(2) Å, c = 13.330(3) Å, β = 111.97(3)°, Z = 2; [Co(taci)2](NO3)2·1.5H2O (3), C12CoH33N8O13.5, monoclinic, space group P21/c, a = 7.081(1) Å, b = 8.743(1) Å, c = 18.181(2) Å, β= 99.49(1)°, Z = 2. All three structures exhibited distorted octahedral MN6 coordination. The stability constants for the complexes [M(taci)]2+ (M = Mn, Fe, Co) and [M(taci)2]2+ (M = Fe, Co) in aqueous media have been evaluated by potentiometric titration. Comparison with other divalent cations showed that the order of stability increases MnII <CdII ≈ FeII <ZnII <CoII <CuII <NiII. In alkaline aqueous media, the complexes 1-3 are readily oxidized by dioxygen. The redox properties were analyzed by a series of polarographic and cyclic voltammetric measurements. A new isomeric form of a bis-taci CoIII complex was formed, where one of the taci ligands coordinates the metal cation by one nitrogen and two oxygen atoms. The complex was isolated in crystalline form as [Co(taci)(Htaci)](NO3)4·0.5H2O (4), C12-CoH32N32O18O18.5, monoclinic, space group C2/c, a = 30.541(3) A, b = 9.015(1) Å, c = 17.852(2) Å, β= 95.63(1)°, Z = 8. [Co(tach)(H2O)x(NO3)3-x] x+ (tach = all-cis-1,3,5-triaminocyclohexane, 0 ≤ x ≤ 3) was used as a model to demonstrate that, for CoIII, the substitution of the three monodentate coligands by a taci molecule resulted generally in an asymmetric binding. An N,O,O and an N,N,O coordination mode were observed for [Co(taci)(tach)](NO3)3·3H2O (5), and [Co(H-itaci)(tach)](NO3)2·(3 - x)H2O·MeOH, 0.2 ≤ x ≤ 0.5 (6), respectively. Crystal data: 5 (C12CoH36N9O15), monoclinic, P21/n, a = 8.942(5) Å, b = 30.07(3) Å, c = 9.354(5) Å, β= 109.25(4)°, Z = 4; 6 (x ≈ 0.2, C12CoH12.2N8O12), monoclinic, P21/n, a = 7.337(2) Å, b = 19.847(4) Å, c = 15.226(3) Å, β= 93.59(3)°, Z = 4.

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VL - 37

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EP - 1008

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

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