The Design of Selective Chelating Agents: 1,3,5‐Trideoxy‐1,3,5‐tris‐(dimethylamino)‐<i>cis</i>‐inositol, a Powerful Ligand for Hard and Highly Charged Metal Ions

Hegetschweiler, Kaspar; Kradolfer, Thomas; Gramlich, Völker; Hancock, Robert D.

doi:10.1002/chem.19950010112

Cited by 32 publications

(58 citation statements)

References 28 publications

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“…These properties are in agreement with the elongation of the MN 6 core along the pseudotrigonal axis. 28 A similar relationship has previously been observed between the structural parameters of bis-taci complexes with an MO 6 coordination. It is interesting, however, that there is no obvious correlation between the C-N-M bond angle and the metal ion size.…”

supporting

confidence: 67%

“…In fact, the oxygen donors of taci are only effective in metal binding if they are deprotonated. 28 For the Co III complex 5, coordination to alkoxo groups is even possible in acidic media, since the noncoordinated amino groups act as an internal base, facilitating the deprotonation of the oxygen donors and generating a zwitterionic form of taci. However, it has recently been shown that, in the case of the divalent Mg 2+ , Ca 2+ , Sr 2+ , and Ba 2+ , the coordinated hydroxy groups are not sufficiently acidic to cause such a proton transfer from O to N and they remain protonated.…”

Section: Preparation and Crystal Structure Of [M(taci) 2 ] 2+ Complexesmentioning

confidence: 99%

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Structure, Stability, and Redox Properties of Mn^II, Fe^II, Co^II, and Co^III Complexes with 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol¹

et al. 1998

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The interaction of Mn II , Fe II , and Co II 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 ](NO 3 ) 2 ‚2H 2 O (1), C 12 H 34 MnN 8 O 14 , monoclinic, space group P2 1 /c, a ) 7.107(5) Å, b ) 8.742(2) Å, c ) 18.527(6) Å, ) 100.20(4)°, Z ) 2; [Fe(taci) 2 ]Cl 2 ‚6H 2 O (2), C 12 Cl 2 FeH 42 N 6 O 12 , monoclinic, space group C2/m, a ) 11.420(2) Å, b ) 9.300 (2) (2) Å, ) 99.49(1)°, Z ) 2. All three structures exhibited distorted octahedral MN 6 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 Mn II < Cd II ≈ Fe II < Zn II < Co II < Cu II < Ni II . 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 Co III 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)](NO 3 ) 4 ‚0.5H 2 O (4), C 12 -CoH 32 N 10 O 18.5 , monoclinic, space group C2/c, a ) 30.541(3) Å, b ) 9.015(1) Å, c ) 17.852(2) Å, ) 95.63-(1)°, Z ) 8. [Co(tach)(H 2 O) x (NO 3 ) 3-x ] x+ (tach ) all-cis-1,3,5-triaminocyclohexane, 0 e x e 3) was used as a model to demonstrate that, for Co III , 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)](NO 3 ) 3 ‚3H 2 O (5), and [Co(H -1 taci)(tach)](NO 3 ) 2 ‚(3 -x)H 2 O‚xMeOH, 0.2 e x e 0.5 (6), respectively. Crystal data: 5 (C 12 CoH 36 N 9 O 15 ), monoclinic, P2 1 /n, a ) 8.942(5) Å, b ) 30.07(3) Å, c ) 9.354(5) Å, ) 109.25(4)°, Z ) 4; 6 (x ≈ 0.2, C 12.2 CoH 35.4 N 8 O 12 ), monoclinic, P2 1 /n, a ) 7.337(2) Å, b ) 19.847(4) Å, c ) 15.226(3) Å, ) 93.59(3)°, Z ) 4.

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supporting

confidence: 67%

Section: Preparation and Crystal Structure Of [M(taci) 2 ] 2+ Complexesmentioning

confidence: 99%

Structure, Stability, and Redox Properties of Mn^II, Fe^II, Co^II, and Co^III Complexes with 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol¹

et al. 1998

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“…In terms of simple VSEPR (valence shell electron pair repulsion) considerations, one would expect strict O h symmetry for an unstrained GeO 6 moiety. Regarding some negative charges on the alkoxo donors, enhanced ligand-ligand repulsion should result in an increase of interligand OÁ Á ÁO distances (Hegetschweiler et al, 1995). As a matter of fact, in all our previous investigations, the interligand OÁ Á ÁO separations have been found to be larger than the corresponding intraligand distances throughout.…”

Section: Resultsmentioning

confidence: 56%

Hydrogen-bonding patterns in bis[2,4,6-triazaniumylcyclohexane-1,3,5-tris(olate)-κ³O,O′,O′′]germanium(IV) tetrachloride hexahydrate

2016

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A first preliminary report on the crystal structure of a hydrated salt formulated as [Ge(taci)2]Cl4·13H2O (taci is 1,3,5-triamino-1,3,5-trideoxy-cis-inositol) appeared more than 20 years ago [Ghisletta (1994). PhD thesis, ETH Zürich. Switzerland]. At that time it was not possible to discriminate unambiguously between the positions of some of the chloride ions and water O atoms, and disorder was thus postulated. In a new determination, a conclusive scheme of hydrogen bonding proves to be a particularly appealing aspect of the structure. Single crystals of the title compound, C12H30GeN6O6(4+)·4Cl(-)·6H2O or [Ge(taci)2]2Cl8·12H2O, were grown from an aqueous solution by slow evaporation of the solvent. The two [Ge(taci)2](4+) cations exhibit a double-adamantane-type structure with exclusive O-atom coordination and approximate D3d symmetry. The taci ligands adopt a zwitterionic form with deprotonated hydroxy groups and protonated amino groups. Both cations are hydrogen bonded to six water molecules. The structure of the hydration shell of the two cations is, however, slightly different. The {[Ge(taci)2]·6H2O}(4+) aggregates are interlinked in all three dimensions by further hydrogen bonds of the types N-H...Cl...H-N, N-H...O(H)2...H-N, (Ge)O...H-O(H)...H-N, N-H...O(H)-H...Cl...H-N, (Ge)O...H-O-H...Cl...H-N, N-H...O(H)-H...Cl...H-(H)O...H-N, (Ge)O...H-O-H...Cl...H-(H)O...H-N and Ge(O)...H-O-H...Cl...H-O-H...O(Ge).

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“…Unfortunately, ES-MS data allowing the confirmation of this 1:1 binding mode between L and Al 3þ ions could not be obtained from solution containing L and Al 3þ . Similarly to the corresponding complex formed with Taci and other derivatives [36][37][38], the formation of a unique electrochemical signal around þ 175 mV indicates that the hard metal cation is coordinated by the alkoxo groups of L, the protons of the hydroxyl groups in L being transferred to the amino groups with formation of ammonium subunits.…”

Section: Electrochemical Behavior Of L In the Presence Of Al 31 Cationsmentioning

confidence: 96%

Electrochemical Signature of the Coordination Mode in Metal Complexes With a tris-Ferrocenyl Derivative of the Taci Ligand

Heitzmann

Bucher

Moutet

et al. 2006

Supramolecular Chemistry

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A new electroactive ligand L built on the Taci (1,3,5-triamino-1,3,5-trideoxy-cis-inositol) platform and bearing three chemically equivalent ferrocene units was prepared and characterized. Electrochemical investigations indicate that electrostatic communication occurs between the three ferrocene groups in L, this electrochemical communication being disrupted in the presence of protons or nucleophilic reagents. Upon addition of metal cations, the electroactivity of L is strongly modified and a remarkable electrochemical signature of the coordination mode adopted by the corresponding complexes is obtained.

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The Design of Selective Chelating Agents: 1,3,5‐Trideoxy‐1,3,5‐tris‐(dimethylamino)‐cis‐inositol, a Powerful Ligand for Hard and Highly Charged Metal Ions

Cited by 32 publications

References 28 publications

Structure, Stability, and Redox Properties of Mn^II, Fe^II, Co^II, and Co^III Complexes with 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol¹

Structure, Stability, and Redox Properties of Mn^II, Fe^II, Co^II, and Co^III Complexes with 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol¹

Hydrogen-bonding patterns in bis[2,4,6-triazaniumylcyclohexane-1,3,5-tris(olate)-κ³O,O′,O′′]germanium(IV) tetrachloride hexahydrate

Electrochemical Signature of the Coordination Mode in Metal Complexes With a tris-Ferrocenyl Derivative of the Taci Ligand

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The Design of Selective Chelating Agents: 1,3,5‐Trideoxy‐1,3,5‐tris‐(dimethylamino)‐cis‐inositol, a Powerful Ligand for Hard and Highly Charged Metal Ions

Cited by 32 publications

References 28 publications

Structure, Stability, and Redox Properties of MnII, FeII, CoII, and CoIII Complexes with 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol1

Structure, Stability, and Redox Properties of MnII, FeII, CoII, and CoIII Complexes with 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol1

Hydrogen-bonding patterns in bis[2,4,6-triazaniumylcyclohexane-1,3,5-tris(olate)-κ3O,O′,O′′]germanium(IV) tetrachloride hexahydrate

Electrochemical Signature of the Coordination Mode in Metal Complexes With a tris-Ferrocenyl Derivative of the Taci Ligand

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Product

Resources

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Structure, Stability, and Redox Properties of Mn^II, Fe^II, Co^II, and Co^III Complexes with 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol¹

Structure, Stability, and Redox Properties of Mn^II, Fe^II, Co^II, and Co^III Complexes with 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol¹

Hydrogen-bonding patterns in bis[2,4,6-triazaniumylcyclohexane-1,3,5-tris(olate)-κ³O,O′,O′′]germanium(IV) tetrachloride hexahydrate