1,3,5‐Triamino‐1,3,5‐trideoxy‐<i>cis</i>‐inositol, a Ligand with a Remarkable Versatility for Metal Ions. Part XIII

Hegetschweiler, Kaspar; Egli, André; Herdtweck, Eberhardt; Herrmann, Wolfgang A.; Alberto, Roger; Gramlich, Völker

doi:10.1002/hlca.200590027

Helvetica Chimica Acta

2005

DOI: 10.1002/hlca.200590027

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1,3,5‐Triamino‐1,3,5‐trideoxy‐cis‐inositol, a Ligand with a Remarkable Versatility for Metal Ions. Part XIII

Kaspar Hegetschweiler

André Egli

Eberhardt Herdtweck

et al.

Abstract: Dedicated to Professor AndreÂ Merbach on the occasion of his 65th birthdayThe two neutral complexes [Re(CO) . The crystal structures of 1 and 2, which were determined by single crystal X-ray analysis, are virtually isomorphous. Both compounds crystallize in the orthorhombic space group Pnma, Z 4; 1: a 14.806(3), b 8.466(2), c 9.781(2) , 2: a 13.050(2), b 8.732(1), c 9.061(1) . In both complexes, the monodeprotonated H À1 taci ligand is bonded to the Re center in an N,O,N-coordination mode. The resulting mole… Show more

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Chelation versus Binucleation: Metal Complex Formation with the Hexadentate all‐cis‐N¹,N²‐Bis(2,4,6‐trihydroxy‐3,5‐diaminocyclohexyl)ethane‐1,2‐diamine

Bartholomä¹,

Gisbrecht²,

Stucky³

et al. 2010

Chemistry A European J

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The hexadentate ligand all-cis-N(1),N(2)-bis(2,4,6-trihydroxy-3,5-diaminocyclohexyl)ethane-1,2-diamine (L(e)) was synthesized in five steps with an overall yield of 39% by using [Ni(taci)(2)]SO(4).4H(2)O as starting material (taci=1,3,5-triamino-1,3,5-trideoxy-cis-inositol). Crystal structures of [Na(0.5)(H(6)L(e))](BiCl(6))(2)Cl(0.5).4H(2)O (1), [Ni(L(e))]Cl(2).5H(2)O (2), [Cu(L(e))](ClO(4))(2).H(2)O (3), [Zn(L(e))]CO(3).7H(2)O (4), [Co(L(e))](ClO(4))(3) (5c), and [Ga(H(-2)L(e))]NO(3).2H(2)O (6) are reported. The Na complex 1 exhibited a chain structure with the Na(+) cations bonded to three hydroxy groups of one taci subunit of the fully protonated H(6)(L(e))(6+) ligand. In 2, 3, 4, and 5c, a mononuclear hexaamine coordination was found. In the Ga complex 6, a mononuclear hexadentate coordination was also observed, but the metal binding occurred through four amino groups and two alkoxo groups of the doubly deprotonated H(-2)(L(e))(2-). The steric strain within the molecular framework of various M(L(e)) isomers was analyzed by means of molecular mechanics calculations. The formation of complexes of L(e) with Mn(II), Cu(II), Zn(II), and Cd(II) was investigated in aqueous solution by using potentiometric and spectrophotometric titration experiments. Extended equilibrium systems comprising a large number of species were observed, such as [M(L(e))](2+), protonated complexes [MH(z)(L(e))](2+z) and oligonuclear aggregates. The pK(a) values of H(6)(L(e))(6+) (25 degrees C, mu=0.10 M) were found to be 2.99, 5.63, 6.72, 7.38, 8.37, and 9.07, and the determined formation constants (log beta) of [M(L(e))](2+) were 6.13(3) (Mn(II)), 20.11(2) (Cu(II)), 13.60(2) (Zn(II)), and 10.43(2) (Cd(II)). The redox potentials (vs. NHE) of the [M(L(e))](3+/2+) couples were elucidated for Co (-0.38 V) and Ni (+0.90 V) by cyclic voltammetry.

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Chelation versus Binucleation: Metal Complex Formation with the Hexadentate all‐cis‐N¹,N²‐Bis(2,4,6‐trihydroxy‐3,5‐diaminocyclohexyl)ethane‐1,2‐diamine

Bartholomä¹,

Gisbrecht²,

Stucky³

et al. 2010

Chemistry A European J

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The Coordination Chemistry of 1,4‐Diazepan‐6‐amine

et al. 2006

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The new, tridentate, facially coordinating ligand 1,4-diazepan-6-amine (daza) has been prepared from ethane-1,2-diamine and 2,3-dibromo-1-propanol in a seven-step procedure with an overall yield of 22 %. The conformation of the free ligand has been elucidated by pH-and temperaturedependent 1 H NMR spectroscopy and by a single-crystal Xray structure analysis of H 3 dazaCl 3 ·H 2 O. A twisted chair with a predominantly equatorial orientation of the primary amino group has been established for daza and its protonation products

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Polymerization of Mo^V: Synthesis and Characterization of a Dinuclear Mo^V and a Hexanuclear Mixed‐Valence Mo^V/Mo^VI Complex

et al. 2007

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1,3,5‐Triamino‐1,3,5‐trideoxy‐cis‐inositol, a Ligand with a Remarkable Versatility for Metal Ions. Part XIII

Cited by 5 publications

References 42 publications

Chelation versus Binucleation: Metal Complex Formation with the Hexadentate all‐cis‐N¹,N²‐Bis(2,4,6‐trihydroxy‐3,5‐diaminocyclohexyl)ethane‐1,2‐diamine

Chelation versus Binucleation: Metal Complex Formation with the Hexadentate all‐cis‐N¹,N²‐Bis(2,4,6‐trihydroxy‐3,5‐diaminocyclohexyl)ethane‐1,2‐diamine

The Coordination Chemistry of 1,4‐Diazepan‐6‐amine

Polymerization of Mo^V: Synthesis and Characterization of a Dinuclear Mo^V and a Hexanuclear Mixed‐Valence Mo^V/Mo^VI Complex

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1,3,5‐Triamino‐1,3,5‐trideoxy‐cis‐inositol, a Ligand with a Remarkable Versatility for Metal Ions. Part XIII

Cited by 5 publications

References 42 publications

Chelation versus Binucleation: Metal Complex Formation with the Hexadentate all‐cis‐N1,N2‐Bis(2,4,6‐trihydroxy‐3,5‐diaminocyclohexyl)ethane‐1,2‐diamine

Chelation versus Binucleation: Metal Complex Formation with the Hexadentate all‐cis‐N1,N2‐Bis(2,4,6‐trihydroxy‐3,5‐diaminocyclohexyl)ethane‐1,2‐diamine

The Coordination Chemistry of 1,4‐Diazepan‐6‐amine

Polymerization of MoV: Synthesis and Characterization of a Dinuclear MoV and a Hexanuclear Mixed‐Valence MoV/MoVI Complex

Contact Info

Product

Resources

About

Chelation versus Binucleation: Metal Complex Formation with the Hexadentate all‐cis‐N¹,N²‐Bis(2,4,6‐trihydroxy‐3,5‐diaminocyclohexyl)ethane‐1,2‐diamine

Chelation versus Binucleation: Metal Complex Formation with the Hexadentate all‐cis‐N¹,N²‐Bis(2,4,6‐trihydroxy‐3,5‐diaminocyclohexyl)ethane‐1,2‐diamine

Polymerization of Mo^V: Synthesis and Characterization of a Dinuclear Mo^V and a Hexanuclear Mixed‐Valence Mo^V/Mo^VI Complex