Dinuclear Amine–Thiophenolate Complexes Coligated by Ferrocenemonocarboxylate and 1,1′‐Ferrocenedicarboxylate Anions: Preparation, Characterization and Structures of Trinuclear [LMII2(O2CC5H4FeCp)]+ and Pentanuclear [(LMII2)2(O2CC5H4)2Fe]2+ Complexes (M=Co, Ni, Zn)

Lozan, Vasile; Buchholz, Axel; Plass, Winfried; Kersting, Berthold

doi:10.1002/chem.200700107

Cited by 31 publications

(16 citation statements)

References 63 publications

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“…The electronic absorption spectrum of complex 2 in chloroform solution shows two www.chemeurj.org low energy bands at 643 and 1131 nm which are typical for octahedral high-spin nickel(II) ions. [25,26] To our knowledge 2 is the first trinuclear nickel(II) complex based on a carbohydrate ligand system.…”

Section: Resultsmentioning

confidence: 99%

Hydrogen Bonds as Structural Directive towards Unusual Polynuclear Complexes: Synthesis, Structure, and Magnetic Properties of Copper(II) and Nickel(II) Complexes with a 2‐Aminoglucose Ligand

Burkhardt

Spielberg

Simon

et al. 2009

Chemistry A European J

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The reaction of benzyl 2-amino-4,6-O-benzylidene-2-deoxy-alpha-D-glucopyranoside (HL) with the metal salts Cu(ClO(4))(2)6 H(2)O and Ni(NO(3))(2)6 H(2)O affords via self-assembly a tetranuclear mu(4)-hydroxido bridged copper(II) complex [(mu(4)-OH)Cu(4)(L)(4)(MeOH)(3)(H(2)O)](ClO(4))(3) (1) and a trinuclear alcoholate bridged nickel(II) complex [Ni(3)(L)(5)(HL)]NO(3) (2), respectively. Both complexes crystallize in the acentric space group P2(1). The X-ray crystal structure reveals the rare (mu(4)-OH)Cu(4)O(4) core for complex 1 which is mu(2)-alcoholate bridged. The copper(II) ions possess a distorted square-pyramidal geometry with an [NO(4)] donor set. The core is stabilized by hydrogen bonding between the coordinating amino group of the glucose backbone and the benzylidene protected oxygen atom O4 of a neighboring {Cu(L)} fragment as hydrogen-bond acceptor. For complex 2 an [N(4)O(2)] donor set is observed at the nickel(II) ions with a distorted octahedral geometry. The trinuclear isosceles Ni(3) core is bridged by mu(3)-alcoholate O3 oxygen atoms of two glucose ligands. The two short edges are capped by mu(2)-alcoholate O3 oxygen atoms of the two ligands coordinated at the nickel(II) ion at the vertex of these two edges. Along the elongated edge of the triangle a strong hydrogen bond (244 pm) between the O3 oxygen atoms of ligands coordinating at the two relevant nickel(II) ions is observed. The coordinating amino groups of the these two glucose ligands are involved in additional hydrogen bonds with O4 oxygen atoms of adjacent ligands further stabilizing the trinuclear core. The carbohydrate backbones in all cases adopt the stable (4)C(1) chair conformation and exhibit the rare chitosan-like trans-2,3-chelation. Temperature dependent magnetic measurements indicate an overall antiferromagnetic behavior for complex 1 with J(1)=-260 and J(2)=-205 cm(-1) (g=2.122). Compound 2 is the first ferromagnetically coupled trinuclear nickel(II) complex with J(A)=16.4 and J(B)=11.0 cm(-1) (g(1,2)=2.183, g(3)=2.247). For the high-spin nickel(II) centers a zero-field splitting of D(1,2)=3.7 cm(-1) and D(3)=1.8 cm(-1) is observed. The S=3 ground state of complex 2 is consistent with magnetization measurements at low temperatures.

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Section: Resultsmentioning

confidence: 99%

Hydrogen Bonds as Structural Directive towards Unusual Polynuclear Complexes: Synthesis, Structure, and Magnetic Properties of Copper(II) and Nickel(II) Complexes with a 2‐Aminoglucose Ligand

Burkhardt

Spielberg

Simon

et al. 2009

Chemistry A European J

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“…Less attention has been paid to the use of discrete dinuclear LM 2 complexes. To our knowledge, these complexes represent the fi rst class of compounds containing dinuclear aminethiolate complexes and redox-active ferrocenecarboxylates in the same molecule [72][73][74][75].…”

Section: Redox-active Ferrocenecarboxylates Anions Coordinated By Dinmentioning

confidence: 99%

“…Mold. 2013, 8 (1), [58][59][60][61][62][63][64][65][66][67][68][69][70][71][72][73][74][75][76][77] ) at 0.71 V, and iii) the oxidation of the thiophenolate sulfur atoms yielding a nickel bound thiyl radical at 1.59 V. Anodic shifts in the second and third redox waves are clearly discernible, confi rming the above fi ndings that the electron transfer events of the ferrocenyl moiety and the binuclear subunit infl uence one another. The fact that the potential shifts are not so pronounced than in 9 is in good agreement with the smaller positive charges of the participating species.…”

Section: Scheme 5 Assignment Of Redox Processes In 9-11 and 14mentioning

confidence: 99%

Dinuclear Complexes as Building Blocks for Tetra-Nuclear Macrocyclic Complexes with Dithiolate Macrocyclic Ligand

Lozan¹

2013

ChemJMold

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A series of novel tri-, tetra-and pentanuclear complexes composed of dinuclear LM 2 units (M=Co, Ni, Zn; L=24-membered macrocyclic hexaaza-dithiophenolate ligand) and ferrocene-carboxylate ([CpFeC 5 H 4 CO 2 ]ˉ), 1,1'-ferro-cenedicarboxylate ([Fe(C 5 Keywords: coordination chemistry, amino-thiophenolate ligands, di-and tetranuclear complexes, ferrocene and naphthalene diimide derivatives, polynuclear complexes IntroductionThe chemistry of container molecules has developed extensively over the past two decades. Many container molecules such as calixarenes, resorcarenes, cyclodextrins, carcerands and glycourils have been invaluable in studying the fundamental principles of inclusion phenomena and consequently their use in separation science or drug delivery, as two examples of application. Importantly, the area has attracted interest in the field of supramolecular chemistry because the properties of such host-guest compounds are often different from those of their constituent components. By adjusting the size and form of the binding cavity it is often possible to complex co-ligands in unusual coordination modes, to activate and transform small molecules, or to stabilize reactive intermediates [1,2]. One subclass are the metallated container molecules, in which metal ions and clusters are used as both a point of recognition and to give the container a well-defined structure. Such compounds also allow for an interplay of molecular recognition and transition-metal catalysis, and for the construction of more effective enzyme mimics. Of interest to the present work is the ability of metallocavitands to recognize and encapsulate difunctionalised molecules towards stabilising or enhancing the optical and electronic properties of redox-and photo-active compounds within a confined environment set up by two hemispheres.The carboxylate group, RCO 2-, can bind to transition metals in a variety of coordination modes giving rise to complexes of great structural diversity [3]. Current activities focus on the coordination chemistry of polycarboxylate ligands, as these offer great potential in the construction of polynuclear aggregates [4] and extended coordination polymers with micro-and mesoporous structures [5][6][7][8] or catalytic properties [9]. In addition, polycarboxylate ligands are of importance as spin-coupling bridging ligands [10][11][12][13][14][15][16][17] in the rapidly expanding fi eld of molecular magnetism [18, 19]. In this context, an enormous amount of literature has been generated concerning the distance dependence of magnetic exchange interactions between metal atoms linked by extended dicarboxylate ligands. Dinuclear copper complexes bridged by oxalate [20, 21] and terephthalate [22][23][24] dianions form, by far, the largest group of such systems, and it appears that the exchange interactions depend on the M···M distance [25], the relative orientation of the magnetic orbitals [26], and the degree of conjugation of the organic spacer unit [27, 28].

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“…[2] Besides dinuclear [M 2 L(μ-O 2 CR)] + structures, [3] we have also reported higher-nuclearity complexes of the type [(M 2 L) 2 (μ-O 2 C-R-CO 2 )] 2+ , in which pairs of bioctahedral [M 2 L] 2+ units are united by a dicarboxylate dianion. [4][5][6] The carboxylato groups in these metal complexes are invariably coordinated in a bridging mode thereby generating bisoctahedral N 3 M(μ-SR) 2 + complexes. The new complexes were characterized by elemental analyses, ESI mass spectrometry, IR and UV/Vis spectroscopy, and by 1 H, 13 C, and 31 P NMR (for Zn).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Pentanuclear Complexes Composed of Pairs of Macrocyclic Ni₂L and Zn₂L Complexes Linked by cis‐[PtCl₂(dppba)₂] and trans‐[RhCl(CO)(dppba)₂] [dppba = (4‐Diphenylphosphanyl)benzoate, L = Macrocyclic Ligand]

Golecki

Kersting

2013

Zeitschrift anorg allge chemie

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Dinuclear Amine–Thiophenolate Complexes Coligated by Ferrocenemonocarboxylate and 1,1′‐Ferrocenedicarboxylate Anions: Preparation, Characterization and Structures of Trinuclear [LM^II₂(O₂CC₅H₄FeCp)]⁺ and Pentanuclear [(LM^II₂)₂(O₂CC₅H₄)₂Fe]²⁺ Complexes (M=Co, Ni, Zn)

Cited by 31 publications

References 63 publications

Hydrogen Bonds as Structural Directive towards Unusual Polynuclear Complexes: Synthesis, Structure, and Magnetic Properties of Copper(II) and Nickel(II) Complexes with a 2‐Aminoglucose Ligand

Hydrogen Bonds as Structural Directive towards Unusual Polynuclear Complexes: Synthesis, Structure, and Magnetic Properties of Copper(II) and Nickel(II) Complexes with a 2‐Aminoglucose Ligand

Dinuclear Complexes as Building Blocks for Tetra-Nuclear Macrocyclic Complexes with Dithiolate Macrocyclic Ligand

Synthesis and Characterization of Pentanuclear Complexes Composed of Pairs of Macrocyclic Ni₂L and Zn₂L Complexes Linked by cis‐[PtCl₂(dppba)₂] and trans‐[RhCl(CO)(dppba)₂] [dppba = (4‐Diphenylphosphanyl)benzoate, L = Macrocyclic Ligand]

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Dinuclear Amine–Thiophenolate Complexes Coligated by Ferrocenemonocarboxylate and 1,1′‐Ferrocenedicarboxylate Anions: Preparation, Characterization and Structures of Trinuclear [LMII2(O2CC5H4FeCp)]+ and Pentanuclear [(LMII2)2(O2CC5H4)2Fe]2+ Complexes (M=Co, Ni, Zn)

Cited by 31 publications

References 63 publications

Hydrogen Bonds as Structural Directive towards Unusual Polynuclear Complexes: Synthesis, Structure, and Magnetic Properties of Copper(II) and Nickel(II) Complexes with a 2‐Aminoglucose Ligand

Hydrogen Bonds as Structural Directive towards Unusual Polynuclear Complexes: Synthesis, Structure, and Magnetic Properties of Copper(II) and Nickel(II) Complexes with a 2‐Aminoglucose Ligand

Dinuclear Complexes as Building Blocks for Tetra-Nuclear Macrocyclic Complexes with Dithiolate Macrocyclic Ligand

Synthesis and Characterization of Pentanuclear Complexes Composed of Pairs of Macrocyclic Ni2L and Zn2L Complexes Linked by cis‐[PtCl2(dppba)2] and trans‐[RhCl(CO)(dppba)2] [dppba = (4‐Diphenylphosphanyl)benzoate, L = Macrocyclic Ligand]

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Dinuclear Amine–Thiophenolate Complexes Coligated by Ferrocenemonocarboxylate and 1,1′‐Ferrocenedicarboxylate Anions: Preparation, Characterization and Structures of Trinuclear [LM^II₂(O₂CC₅H₄FeCp)]⁺ and Pentanuclear [(LM^II₂)₂(O₂CC₅H₄)₂Fe]²⁺ Complexes (M=Co, Ni, Zn)

Synthesis and Characterization of Pentanuclear Complexes Composed of Pairs of Macrocyclic Ni₂L and Zn₂L Complexes Linked by cis‐[PtCl₂(dppba)₂] and trans‐[RhCl(CO)(dppba)₂] [dppba = (4‐Diphenylphosphanyl)benzoate, L = Macrocyclic Ligand]