Neuartige (η<sup>2</sup>‐Alkin)kupfer(I)‐carboxylat‐Komplexe

Lang, Heinrich; Köhler, Katrin; Zsolnai, László

doi:10.1002/cber.19951280514

Cited by 31 publications

(22 citation statements)

References 28 publications

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“…These bond lengths again indicate a stronger interaction of the Cu centers with the acetylenic triple bonds compared to that in 5, although the bend-back angle in 14 of 19 (2) 4 ], [20, 21c, 30] in which the four Cu atoms form (strongly) distorted tetrahedra (Table 3). Although in [(Me 3 SiCCSiMe 3 ) 2 -Cu 4 (m-O 2 CMe) 4 ] [31] a planar arrangement of the four Cu atoms is found, the Cu ± Cu distances are equal in contrast to 13 and 14.…”

Section: 14 (Figures 4 and 5)contrasting

confidence: 50%

Coordination Chemistry of Pentacarbonylrheniumacetylide Complexes with Copper, Silver, and Gold(I): (OC)5ReC≡CRe(CO)5 as Ligand

Mihan¹,

Sünkel²,

Beck³

1999

Chem. Eur. J.

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Section: 14 (Figures 4 and 5)contrasting

confidence: 50%

Coordination Chemistry of Pentacarbonylrheniumacetylide Complexes with Copper, Silver, and Gold(I): (OC)5ReC≡CRe(CO)5 as Ligand

Mihan¹,

Sünkel²,

Beck³

1999

Chem. Eur. J.

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“…In contrast to À or BPh 4 À ), and the ferrocene derivatives. The ferrocenecarboxylates in 6-10 give rise to two characteristic bands, as in other carboxylato-complexes, [30,31] in the 1575-1565 cm À1 and 1435-1425 cm…”

Section: A C H T U N G T R E N N U N G (M-cl)]mentioning

confidence: 98%

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)

Lozan

Buchholz

Plass

et al. 2007

Chemistry A European J

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A series of novel tri- and pentanuclear complexes composed of dinuclear LM(2) units (M=Co, Ni, Zn; L=24-membered macrocyclic hexaazadithiophenolate ligand) and ferrocenecarboxylate ([CpFeC(5)H(4)CO(2)](-)) or 1,1'-ferrocenedicarboxylate ([Fe(C(5)H(4)CO(2))(2)](2-)) groups is reported. The complexes [LM(II) (2)(O(2)CC(5)H(4)FeCp)](+) (M=Co (6), Ni (7), Zn (8)) and [(LM(II) (2))(2)(O(2)CC(5)H(4))(2)Fe](2+) (M=Co (9), Ni (10)) have been prepared by substitution reactions from labile [LM(II) (2)L'](+) precursors (L'=Cl, OAc) and the respective ferrocenecarboxylate anions in methanol. Mixed-valent [(LCo(II)Co(III))(2)(O(2)CC(5)H(4))(2)Fe](4+) (11) was prepared by oxidation of 9 with bromine. Complexes 7[BPh(4)], 8[BPh(4)], 9[BPh(4)](2), 10[BPh(4)](2), and 11[ClO(4)](4) have been characterized by X-ray crystallography; showing that the ferrocenyl carboxylates act as bidentate (7, 8) or bis-bidentate (9-11) bridging ligands towards one or two bioctahedral LM(2) subunits, respectively. The structures are retained in solution as indicated by NMR spectroscopic studies on the diamagnetic Zn(2)Fe complex 8[ClO(4)]. Electrochemical studies reveal significant anodic potential shifts for the oxidation potential of the ferrocenyl moieties upon complexation and the magnitude of the potential shift appears to correlate with the charge of the LM(2) subunits. This is qualitatively explained in terms of destabilizing electrostatic (Coulomb) interactions between the M(2+) ions of the LM(2) unit and the proximate ferrocenium fragment. An analysis of the temperature-dependent magnetic susceptibility data for 10[BPh(4)](2) shows the presence of weak ferromagnetic magnetic exchange interactions between the Ni(II) ions in the LNi(2) units. The exchange coupling across the ferrocenedicarboxylate bridge is negligible.

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“…Two types of complexes were considered: trinuclear [LM + (M=Ni 1, Co 2) with triethylammonium ferrocenylmono-carboxylate (prepared in situ from CpFeC 5 H 4 CO 2 H and triethylamine) in a 1:3 ratio in methanol at room temperature and isolated as perchlorate salts upon addition of LiClO 4 . It should be noted that these reactions are not simple substitution reactions, because a simultaneous conformational change of the supporting ligand from a "partial-cone" to a "bowl-shaped" conformation takes place [76]. Since a chloro-bridged dizinc complex [LZn 2+ fragments is a clean and facile step driven forward by the low solubility of the products.…”

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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Neuartige (η²‐Alkin)kupfer(I)‐carboxylat‐Komplexe

Cited by 31 publications

References 28 publications

Coordination Chemistry of Pentacarbonylrheniumacetylide Complexes with Copper, Silver, and Gold(I): (OC)5ReC≡CRe(CO)5 as Ligand

Coordination Chemistry of Pentacarbonylrheniumacetylide Complexes with Copper, Silver, and Gold(I): (OC)5ReC≡CRe(CO)5 as Ligand

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)

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

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Neuartige (η2‐Alkin)kupfer(I)‐carboxylat‐Komplexe

Cited by 31 publications

References 28 publications

Coordination Chemistry of Pentacarbonylrheniumacetylide Complexes with Copper, Silver, and Gold(I): (OC)5ReC≡CRe(CO)5 as Ligand

Coordination Chemistry of Pentacarbonylrheniumacetylide Complexes with Copper, Silver, and Gold(I): (OC)5ReC≡CRe(CO)5 as Ligand

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)

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

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Neuartige (η²‐Alkin)kupfer(I)‐carboxylat‐Komplexe

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)