Alkaliisocyanacetate. Synthese und Struktur von [K(18‐Krone‐6)](O<sub>2</sub>CCH<sub>2</sub>NC)

Fehlhammer, Wolf Peter; Schrölkamp, Stephan; Hoyer, M.; Hartl, Hans; Beck, Wolfgang

doi:10.1002/zaac.200500258

Cited by 9 publications

(7 citation statements)

References 12 publications

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“…Although it is well-known that Li, Na, and K salts form stable complexes with 12-crown-4, 15-crown-5, and 18-crown-6 ethers, respectively, ,,,, the ionic radius of Li + cation is slightly larger than the cavity size of 12-crown-4 ether. In fact, binary mixtures of 12-crown-4 ethers and certain Li salts form 2:1 sandwich complexes even when an equimolar mixture was prepared .…”

Section: Results and Discussionmentioning

confidence: 98%

Phase Diagrams and Solvate Structures of Binary Mixtures of Glymes and Na Salts

et al. 2013

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We prepared a series of binary mixtures composed of selected Na salts and glymes (tetraglyme, G4, and pentaglyme, G5) with different salt concentrations and anionic species ([X](-): [N(SO2CF3)2](-) = [TFSA](-), [N(SO2F)2](-) = [FSA](-), ClO4(-), PF6(-)) and studied the effects of concentration, anionic structure, and glyme chain length on their phase diagrams and solvate structures. The phase diagrams clearly illustrate that all the mixtures form 1:1 complexes, [Na(G4 or G5)1][X]. The thermal stability of the equimolar mixtures was drastically improved in comparison with those of diluted systems, indicating that all the glyme molecules coordinate to Na(+) cations to form equimolar complexes. Single-crystal X-ray crystallography revealed that [Na(G5)1][X] forms characteristic solvate structures in the crystalline state irrespective of the paired anion species. A comparison of the solvate structures of the glyme-Na complexes with those of the glyme-Li complexes suggests that the ionic radii of the coordinated alkali-metal cations have substantial effects on the resulting solvate structures. The Raman bands of the complex cations were assigned by quantum chemical calculations. Concentration dependencies of cationic and anionic Raman spectra show good agreement with the corresponding phase diagrams. In addition, the Raman spectra of the 1:1 complexes strongly suggest that the glymes coordinate to Na(+) cation in the same way in both liquid and crystalline states. However, the aggregated structure in the crystalline state is broken by melting, which is accompanied by a change in the anion coordination.

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Section: Results and Discussionmentioning

confidence: 98%

Phase Diagrams and Solvate Structures of Binary Mixtures of Glymes and Na Salts

et al. 2013

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“…This lack of solubility was expected to be corrected at later stages by the use of their anionic forms CNCR 2 COOM (M + = Li + , Na +• ). 56,57 However, the instability of the CNR complexes in aqueous media discouraged such experiments.…”

Section: Discussionmentioning

confidence: 99%

A contribution to the rational design of Ru(CO)₃Cl₂L complexes for in vivo delivery of CO

et al. 2015

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A few ruthenium based metal carbonyl complexes, e.g. CORM-2 and CORM-3, have therapeutic activity attributed to their ability to deliver CO to biological targets. In this work, a series of related complexes with the formula [Ru(CO)3Cl2L] (L = DMSO (3), L-H3CSO(CH2)2CH(NH2)CO2H) (6a); D,L-H3CSO(CH2)2CH(NH2)CO2H (6b); 3-NC5H4(CH2)2SO3Na (7); 4-NC5H4(CH2)2SO3Na (8); PTA (9); DAPTA (10); H3CS(CH2)2CH(OH)CO2H (11); CNCMe2CO2Me (12); CNCMeEtCO2Me (13); CN(c-C3H4)CO2Et) (14)) were designed, synthesized and studied. The effects of L on their stability, CO release profile, cytotoxicity and anti-inflammatory properties are described. The stability in aqueous solution depends on the nature of L as shown using HPLC and LC-MS studies. The isocyanide derivatives are the least stable complexes, and the S-bound methionine oxide derivative is the more stable one. The complexes do not release CO gas to the headspace, but release CO2 instead. X-ray diffraction of crystals of the model protein Hen Egg White Lysozyme soaked with 6b (4UWN) and 8 (4UWN) shows the addition of Ru(II)(CO)(H2O)4 at the His15 binding site. Soakings with 7(4UWN) produced the metallacarboxylate [Ru(COOH)(CO)(H2O)3](+) bound to the His15 site. The aqueous chemistry of these complexes is governed by the water-gas shift reaction initiated with the nucleophilic attack of HO(-) on coordinated CO. DFT calculations show this addition to be essentially barrierless. The complexes have low cytotoxicity and low hemolytic indices. Following i.v. administration of CORM-3, the in vivo bio-distribution of CO differs from that obtained with CO inhalation or with heme oxygenase stimulation. A mechanism for CO transport and delivery from these complexes is proposed.

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“…), and thiocyanate (SCN À ), were selected as the parent salts to investigate the anionic (Lewis basicity) effect on the characteristics of the complexes. On the basis of the preferential coordination number and high affinity of 18-crown-6 ether with K + cations, [38][39][40][41] these K salts were complexed with pentaglyme (G5), in which six oxygen atoms are involved within a single molecule, hereafter abbreviated as [K(G5) n ]X based on the molar ratio of the K salt and G5.…”

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confidence: 99%

Pentaglyme–K salt binary mixtures: phase behavior, solvate structures, and physicochemical properties

Mandai

Tsuzuki

Ueno

et al. 2015

Phys. Chem. Chem. Phys.

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We prepared a series of binary mixtures composed of certain K salts (KX) and pentaglyme (G5) with different salt concentrations and anionic species ([X](-): [(CF3SO2)2N](-) = [TFSA](-), [CF3SO3](-) = [TfO](-), [C4F9SO3](-) = [NfO](-), PF6(-), SCN(-)), and characterized them with respect to their phase diagrams, solvate structures, and physicochemical properties. Their phase diagrams and thermal stability strongly implied the formation of equimolar complexes. Single-crystal X-ray crystallography was performed on certain equimolar complexes, which revealed that G5 molecules coordinate to K(+) cations in a characteristic manner, like 18-crown-6 ether in the crystalline state, irrespective of the paired anions. The solvate structures in the molten state were elucidated by a combination of temperature-dependent Raman spectroscopy and X-ray crystallography. A drastic spectral variation was observed in the [K(G5)1][TfO] Raman spectra, indicating that solvate structures in the crystalline state break apart upon melting. The solvate stability of [K(G5)1]X is closely related to the ion-ion interaction of the parent salts. A stable solvate forms when the ion-dipole interaction between K(+) and G5 overwhelms the ion-ion interaction between K(+) and X(-). Furthermore, the physicochemical properties of certain equimolar mixtures were evaluated. A Walden plot clearly reflects the ionic nature of the molten equimolar complexes. Judging from the structural characteristics and dissociativity, we classified [K(G5)1]X into two groups, good and poor solvate ionic liquids.

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Alkaliisocyanacetate. Synthese und Struktur von [K(18‐Krone‐6)](O₂CCH₂NC)

Cited by 9 publications

References 12 publications

Phase Diagrams and Solvate Structures of Binary Mixtures of Glymes and Na Salts

Phase Diagrams and Solvate Structures of Binary Mixtures of Glymes and Na Salts

A contribution to the rational design of Ru(CO)₃Cl₂L complexes for in vivo delivery of CO

Pentaglyme–K salt binary mixtures: phase behavior, solvate structures, and physicochemical properties

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Alkaliisocyanacetate. Synthese und Struktur von [K(18‐Krone‐6)](O2CCH2NC)

Cited by 9 publications

References 12 publications

Phase Diagrams and Solvate Structures of Binary Mixtures of Glymes and Na Salts

Phase Diagrams and Solvate Structures of Binary Mixtures of Glymes and Na Salts

A contribution to the rational design of Ru(CO)3Cl2L complexes for in vivo delivery of CO

Pentaglyme–K salt binary mixtures: phase behavior, solvate structures, and physicochemical properties

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Product

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Alkaliisocyanacetate. Synthese und Struktur von [K(18‐Krone‐6)](O₂CCH₂NC)

A contribution to the rational design of Ru(CO)₃Cl₂L complexes for in vivo delivery of CO