Copper(ii) Coordination Compounds: Classification and Analysis of Crystallographic and Structural Data Ii. Mononuclear-, Hexa-, Hepta-and Octacoordinate Compounds

Melnı́k, Milan; Kabešová, M.; Dunaj‐Jurčo, M.; Holloway, Clive Ε.

doi:10.1080/00958979808027143

Cited by 45 publications

(11 citation statements)

References 378 publications

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“…[9,24,25,28] [Cu(L e )] 2 + exhibited the usual tetragonally elongated 4 + 2 Jahn-Teller geometry. [29] In solution, the hexaamine structure of these complexes was retained as indicated by the UV/Vis parameters for [Co H NMR spectra exhibited six and eight resonances, [30] respectively, with two separate signals for the CH 2 hydrogen atoms of the ethylene bridge, indicating a chiral C 2 symmetry for the solution structure. In contrast to the labile Ni II , Cu II and Zn II complexes, that readily decay in acidic media (vide infra), the inert hexaamine structure of [Co (L e )] 3 + is, as expected, unaffected for prolonged periods of time even in 6 m HCl.…”

Section: Resultsmentioning

confidence: 99%

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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Section: Resultsmentioning

confidence: 99%

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 Cu II complex 6 2 showed a characteristic static Jahn ± Teller distortion with four short, equatorial CuÀN bonds (4 exocyclic nitrogen donors, mean Cu À N bond length: 2.05 ) and two long, axial Cu À N bonds (2 endocyclic nitrogen donors, mean CuÀN bond length: 2.41 ). [22] The use of CuCl 2 and CdCl 2 in the above-mentioned preparation procedure resulted in the isolation of the 1:1 complexes [Cu(dapi)Cl 2 ] (7) and [{Cd(dapi)Cl 2 } 2 ] (8). The former is a mononuclear complex with a distorted square-pyramidal coordinated Cu II , whereas the latter is a dimeric species with a roughly octahedral Cd II , with two terminal and two bridging Cl À ligands ( Figure 6).…”

Section: Resultsmentioning

confidence: 99%

The Coordination Chemistry ofcis-3,5-Diaminopiperidine and Substituted Derivatives

et al. 2000

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An efficient and convenient method for the preparation of cis-3,5-diaminopiperidine (dapi) has been established and the coordination chemistry of this ligand with CoII, CoIII, NiII, CuII, ZnII, and CdII has been investigated in the solid state and in aqueous solution. Potentiometric measurements revealed a generally high stability for the bis complexes of the divalent cations with maximum stability for NiII (log beta2 = 21.2, beta2 = [M(dapi)2][M](-1)[dapi](-2), 25 degrees C, mu = 0.1 mol dm(-3)). Cyclic voltammetry established quasi-reversible formation of [Ni(dapi)2]3+ with a redox potential of 0.91 V (versus NHE) for the Ni(II/III) couple. [Co(dapi)2]3+ was prepared by aerial oxidation of the corresponding CoII precursor. The two isomers trans-[Co(dapi)2]3+ (1(3+), 26%) and cis-[Co(dapi)2]3+ (2(3+), 74%), have been separated and isolated as solid Cl- and CF3SO3- salts. In a non-aqueous medium 1(3+) and 2(3+) reacted with paraformaldehyde and NEt3 to give the methylidene-imino derivatives 3(3+) and 4(3+), in which the two piperidine rings are bridged by two or one N-CH2-O-CH2-N bridges, respectively. Crystal structure analyses were performed for H3dapi[ZnCl4]Cl, 1Cl3 x 2H2O, 2Cl3 x H2O, 3[ZnCl4]Cl, 4[ZnCl4]Cl, [Ni(dapi)2]Cl2 x H2O, [Cu(dapi)2](NO3)2, [Cu(dapi)Cl2], [(dapi)ClCd-(mu2-Cl)2-CdCl(dapi)], and [Co(dapi)(NO2)(CO3)]. The stability of [M(II)(dapi)]2+ and [M(II)(dapi)2]2+ complexes in aqueous solution, particularly the remarkably high tendency of [M(dapi)]2+ to undergo coordinative disproportionation is discussed in terms of the specific steric requirements of this ligand. Molecular mechanics calculations have been performed to analyze the different types of strain in these complexes. A variety of alkylated derivatives of dapi have been prepared by reductive alkylation with formaldehyde, benzaldehyde, salicylaldehyde, and pyridine-2-carbaldehyde. The NiII complexes of the pentadentate N3,N5-bis(2-pyridinylmethyl)-cis-3,5-diaminopiperidine (py2dapi) and the hexadentate N3,N5,1-tris(2-pyridinylmethyl)-cis-3,5-diaminopiperidine (py3dapi) have been isolated as crystalline ClO4- salts [Ni(py2dapi)Cl]ClO4 and [Ni(py3dapi)](ClO4)2 x H2O and characterized by crystal structure analyses.

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“…[3] No pair of compounds with the same coordinated ligands -one with the OϪCuϪO unit as the JahnϪTeller axis and the other with the NϪCuϪN as the JahnϪTeller axis -have been reported. [1,2] The absence of isomers is probably due to steric effects of the ligands, which favour only one of the arrangement types in the coordination sphere. With a special ligand shape, different configurations around the central copper ion may be expected.…”

Section: Introductionmentioning

confidence: 99%

“…the axis with the longest CuϪL bonds, coincides with the OϪCuϪO bond in the elongated distorted octahedron. [1,2] A search of the Cambridge Structural Database revealed that in only 9 of the 277 CuN 4 O 2 chromophores does the JahnϪTeller axis coincide with one of the NϪCuϪN bonds, and there is only one example of a compressed octahedron (four longer and two shorter bonds). [3] No pair of compounds with the same coordinated ligands -one with the OϪCuϪO unit as the JahnϪTeller axis and the other with the NϪCuϪN as the JahnϪTeller axis -have been reported.…”

Section: Introductionmentioning

confidence: 99%

Unprecedented Change of the Jahn−Teller Axis in a Centrosymmetric Cu^II Complex Induced by Lattice Water Molecules − Crystal and Molecular Structures of Bis[bis(3,5‐dimethylpyrazol‐1‐yl)acetato]copper(II) and Its Dihydrate

et al. 2002

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Two copper coordination compounds with the tridentate (NON) ligand bis(3,5‐dimethylpyrazol‐1‐yl)acetic acid (Hbdmpza) are reported. The central coordination sphere in both compounds is fulfilled by two ligands in [CuL2]. The ligands are centrosymmetrically oriented around the copper ion, thus forming a trans‐CuN4O2 elongated octahedral chromophore. The atoms in both compounds are not positioned at the same places in the Jahn−Teller‐distorted octahedral environment. For compound [CuL2] (1) two nitrogen atoms are located on the longer axis [Cu−N: 2.438(2) Å], while the other two nitrogen atoms [Cu−N: 2.006(2) Å] and the two oxygen atoms [Cu−O: 1.983(2) Å] form the basal plane of the octahedron. The coordination sphere for [CuL2]·2H2O (2) is composed of four nitrogen atoms [Cu−N: 2.013(3), 2.038(2) Å] that form the basal plane, while the two oxygen atoms are at a longer distance [Cu−O: 2.293(2) Å]. The water molecules in 2 are hydrogen bonded to the non‐coordinated carboxylate oxygen atoms, forming bridges between two neighbouring monomeric units and leading to an infinite chain. Significant differences are observed for both compounds by spectroscopic investigations (EPR, IR, ligand field). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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Copper(ii) Coordination Compounds: Classification and Analysis of Crystallographic and Structural Data Ii. Mononuclear-, Hexa-, Hepta-and Octacoordinate Compounds

Cited by 45 publications

References 378 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 ofcis-3,5-Diaminopiperidine and Substituted Derivatives

Unprecedented Change of the Jahn−Teller Axis in a Centrosymmetric Cu^II Complex Induced by Lattice Water Molecules − Crystal and Molecular Structures of Bis[bis(3,5‐dimethylpyrazol‐1‐yl)acetato]copper(II) and Its Dihydrate

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Copper(ii) Coordination Compounds: Classification and Analysis of Crystallographic and Structural Data Ii. Mononuclear-, Hexa-, Hepta-and Octacoordinate Compounds

Cited by 45 publications

References 378 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 ofcis-3,5-Diaminopiperidine and Substituted Derivatives

Unprecedented Change of the Jahn−Teller Axis in a Centrosymmetric CuII Complex Induced by Lattice Water Molecules − Crystal and Molecular Structures of Bis[bis(3,5‐dimethylpyrazol‐1‐yl)acetato]copper(II) and Its Dihydrate

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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

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

Unprecedented Change of the Jahn−Teller Axis in a Centrosymmetric Cu^II Complex Induced by Lattice Water Molecules − Crystal and Molecular Structures of Bis[bis(3,5‐dimethylpyrazol‐1‐yl)acetato]copper(II) and Its Dihydrate