<i>cis</i>‐Bromierung von eingekapselten Alkenen

Steinfeld, Gunther; Lozan, Vasile; Kersting, Berthold

doi:10.1002/ange.200351131

Cited by 24 publications

(19 citation statements)

References 23 publications

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“…The observed values closely compare with those of 4 and 5 again consistent with pseudo-octahedral N 3 S 2 O coordination environments around the metal atoms [69,70] + cations, tetraphenylborate anions, and acetonitrile molecules of solvent of crystallization. An ORTEP representation of the molecular structure of 9 is shown in Figure 5.…”

Section: Redox-active Ferrocenecarboxylates Anions Coordinated By Dinsupporting

confidence: 71%

“…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%

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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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Section: Redox-active Ferrocenecarboxylates Anions Coordinated By Dinsupporting

confidence: 71%

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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“…[2] These complexes have a rich coordination chemistry since the [(L Me )M 2 ] 2+ fragments are able to coordinate a large variety of coligands LЈ. These include Cl -, [3] OH -, [4] NO 2 -, NO 3 -, N 3 -, [5] BH 4 -, [6] various carboxylates, [7][8][9] N 2 H 4 , pyrazolate, and pyridazine, [5] and some biologically relevant molecules such as HCO 3 -, (p-NO 2 C 6 H 4 O) 2 PO 2 -, and proline. [10] In earlier work, we have also described the synthesis of a few [ + have been reported.…”

Section: (Lј)]mentioning

confidence: 99%

Preparation and Characterization of Dinuclear Ni^II Amine‐Thiophenolate Complexes Coligated by EO₄^– (E = Cl, Re) and EO₄^2– Oxoanions (E = S, Cr, Mo, W)

Lozan

Kersting

2007

Eur J Inorg Chem

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“…[24] Indeed, when 3A C H T U N G T R E N N U N G [ClO 4 ] is treated with a 10-fold excess of triethylammonium ferrocenecarboxylate in methanol at room temperature an exchange reaction takes place and 8A C H T U N G T R E N N U N G [ClO 4 ] can be isolated as an analytically pure yellow powder after workup. The three perchlorate salts 4 ] are air-stable solids that are readily soluble in polar aprotic organic solvents such as dimethylformamide, dichloromethane, acetone and acetonitrile but only slightly soluble in methanol or ethanol.…”

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

confidence: 99%

“…[22][23][24] The extensive redox chemistry exhibited by these dinuclear amine-thiolate complexes [25] and the possibility of coupling these units into polynuclear arrays, led us to synthesize derivatives bearing ferrocenemono-and ferrocenedicarboxylate anions ( complexes. Their preparation, crystal structure determination, spectroscopic, magnetic, and electrochemical properties are reported here.…”

Section: Introductionmentioning

confidence: 99%

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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cis‐Bromierung von eingekapselten Alkenen

Cited by 24 publications

References 23 publications

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

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

Preparation and Characterization of Dinuclear Ni^II Amine‐Thiophenolate Complexes Coligated by EO₄^– (E = Cl, Re) and EO₄^2– Oxoanions (E = S, Cr, Mo, W)

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)

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cis‐Bromierung von eingekapselten Alkenen

Cited by 24 publications

References 23 publications

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

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

Preparation and Characterization of Dinuclear NiII Amine‐Thiophenolate Complexes Coligated by EO4– (E = Cl, Re) and EO42– Oxoanions (E = S, Cr, Mo, W)

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)

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Preparation and Characterization of Dinuclear Ni^II Amine‐Thiophenolate Complexes Coligated by EO₄^– (E = Cl, Re) and EO₄^2– Oxoanions (E = S, Cr, Mo, W)

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)