Untersuchungen mit wasserfreiem Silberfluoroborat und Kupfer(I)‐fluoroborat

Meerwein, Hans; Hederich, Volker; Wunderlich, Klaus

doi:10.1002/ardp.19582911103

Cited by 125 publications

(23 citation statements)

References 9 publications

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“…8 [Cu(NCR) 4 ](X) (X = ClO 4 , BF 4 ; R = Alk, Ar, CHQCH 2 ) species have been prepared by the reaction of CuClO 4 with excess NCR 9 and upon treatment of Cu 2 O with BF 3 ÁEt 2 O in appropriate nitrile solvents. 10 The acetonitrile complexes [Cu(NCMe) 4 ](X) were synthesized by oxidation of metallic copper in acetonitrile using silver 11 or nitrosonium salts 12 or electrolytic oxidation, 11a,12 by reduction of copper(II) salts in MeCN, 12 and also by the reaction of copper(I) precursors (Cu 2 O in the presence of HClO 4 or CuCl) with MeCN. 8a,13 Dialkylcyanamides, as compared to conventional nitriles, are stronger s-donors 3b and consequently they are better ligands toward Cu I centers.…”

Section: Resultsmentioning

confidence: 99%

A novel family of homoleptic copper(i) complexes featuring disubstituted cyanamides: a combined synthetic, structural, and theoretical study

et al. 2017

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Section: Resultsmentioning

confidence: 99%

A novel family of homoleptic copper(i) complexes featuring disubstituted cyanamides: a combined synthetic, structural, and theoretical study

et al. 2017

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“…± Materials. Ligands L and L' were synthesized according to previously published procedures [41], and [Cu(CH 3 CN) 4 )[BF 4 ] was prepared according to the method in [43]. The solvent selected for this work was a ternary mixture of solvents, MeCN/H 2 O/CH 2 Cl 2 80 : 15 : 5 (v/v), in which the ligands (CH 2 Cl 2 , Merck, Uvasol), the copper salt (MeCN, Merck, Uvasol), and Et 4 NCN (H 2 O, Fluka), which was used for decomplexation studies, are soluble.…”

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confidence: 99%

Self-Assembly of Tricuprous Double Helicates: Thermodynamics, Kinetics, and Mechanism

Fatin‐Rouge¹,

Blanc²,

Pfeil

et al. 2001

HCA

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Dedicated to Edgar Heilbronner on the occasion of his 80th birthdayWe report in this paper the coordination and kinetic properties of two oligobipyridine strands, which contain three 2,2'-bipyridine subunits separated by oxydimethylene bridges, the 4,4'-bis(CONET 2 )-substituted L and the 4,4'-bis(CO 2 Et)-substituted L'. Spectrophotometric measurements allowed the characterization of thermodynamic complexes and kinetic intermediates* which are involved in the self-assembly process of L 2 Cu 3 and L ' 2 Cu 3 helicates. The reaction presents positive cooperativity for the binding of two 2,2'-bipyridine strands to the cuprous cations. While reactive kinetic intermediates* present distorted coordination geometries around Cu I , the final rearrangement of the tricuprous bistranded helicates allows more closely tetrahedral coordination of each cation and reduces the interactions. Differences in the bulkiness and electronic properties of the L and L' substituents do not affect significantly the stability of the corresponding helicates, but greatly influence binding rates in the self-assembly process.Introduction. ± In recent years, creating molecules that are programmed by virtue of their structure and binding sites to spontaneously organize themselves into supramolecular architectures held together by metal coordination has aroused the interest of chemists [1 ± 5] (for recent reviews on metal-ion-mediated self-assembly, see, e.g., [2] ], were generated. To design such species presenting specific structural and functional features, it is of great importance to establish the rules by which control the assembly process can be achieved through chemical programming by means of suitable components and assembling algorithms [1] [5]. In the self-assembly of helicates, three main structural features determine the nature and shape of the helical species formed. The binding sites impose the number of strands able to coordinate metal ions with a given geometry. Bidentate or tridendate subunits combined, respectively, with metal ions of tetrahedral [6] [7] and of octahedral [6] [24] coordination geometry produce double helical polynuclear species, while triple helical complexes are formed with bidentate ligands and octahedrally coordinated metal ions [25]. Taking into account these properties, double-helical mixed-valence [14] heteronuclear [26] or heterostranded [27] complexes have been synthesized. However, not every combination of oligomultidentate ligands with metal ions will give helical structures, and the spacers between the metal binding sites play an important role. They should be flexible enough to allow the ligand to bind

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“…After removal of the solvent, the residue was extracted into CHC1, and purified by chromatography on silica gel (eluent: CH,CI,/MeOH, 10: 1) ( [6] in 15 mL of degassed CH,CN was added to 2 (132 mg, 0.1 mmol) in 20 mL of degassed DMF with stirring under argon. The solution turned red-brown.…”

Section: Methodsmentioning

confidence: 99%

Endoreceptors with Convergent Phenanthroline Units: A Molecular Cavity for Six Guest Molecules

Vögtle

Lüer

Balzani

et al. 1991

Angew. Chem. Int. Ed. Engl.

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the Ag'-Ag' distances are 493 and 490pm. Finally, the N-Ag' distances to the bipyridine N atoms are 244-251 pm. The coordination sphere around the central Ag' ion can be regarded as a distorted octahedron, that around each of the two other Ag' ions as a heavily distorted trigonal pyramid.A mononucleari' O1 and two dinucleari3"] Ag' complexes of related macrobicyclic ligands have been reported earlier. The cryptate 6 constitutes the first trinuclear Ag' complex. The three metal ions are arranged in a row, held at well-defined distances, and bound in two different environments, the central one being a tris-bipyridine Ag' site. Cryptand 3 offers the possibility of preparing homo-or heterometallic trinuclear metal cryptates that should display different binding, electrochemical, and photophysical properties for the terminal and the central metal ions, making available a range of novel features. For instance, a Cu'-Ag'-Cu' heterodinuclear complex has already been prepared. Further development of the present work will also include the encapsulation of organic substrates inside the cavities of macrobicycles 3 and 4 either as free bases or as protonated and alkylated derivatives. Experimental Procedures 3:To a stirred solution of Tren (1: 0.047 g, 0.32 mmol) in 5 mL of anhydrous acetonitrile was added dropwise at room temperature under argon a suspension of the dialdehyde 2 (colorless crystals, m.p. 228 "C; 0.1 g, 0.47 mmol) in acetonitrile ( 5 mL). The orange solid was filtered and recrystallized from methanol. Colorless crystals; m.p. 280°C (CH,OH); yield 78%; UV-VIS (CHCIJ CH,OH. 99:l): i .,,, [nm] ( E )

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Untersuchungen mit wasserfreiem Silberfluoroborat und Kupfer(I)‐fluoroborat

Cited by 125 publications

References 9 publications

A novel family of homoleptic copper(i) complexes featuring disubstituted cyanamides: a combined synthetic, structural, and theoretical study

A novel family of homoleptic copper(i) complexes featuring disubstituted cyanamides: a combined synthetic, structural, and theoretical study

Self-Assembly of Tricuprous Double Helicates: Thermodynamics, Kinetics, and Mechanism

Endoreceptors with Convergent Phenanthroline Units: A Molecular Cavity for Six Guest Molecules

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