Cube-type nitrido complexes containing titanium and alkali/alkaline-earth metals

Treatment of [[Ti(eta(5)-C(5)Me(5))(mu-NH)](3)(mu(3)-N)] with alkali-metal bis(trimethylsilyl)amido derivatives [M[N(SiMe(3))(2)]] in toluene affords edge-linked double-cube nitrido complexes [M(mu(4)-N)(mu(3)-NH)(2)[Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)]](2) (M = Li, Na, K, Rb, Cs) or corner-shared double-cube nitrido complexes [M(mu(3)-N)(mu(3)-NH)(5)[Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)](2)] (M = Na, K, Rb, Cs). Analogous reactions with 1/2 equiv of alkaline-earth bis(trimethylsilyl)amido derivatives [M[N(SiMe(3))(2)](2)(thf)(2)] give corner-shared double-cube nitrido complexes [M[(mu(3)-N)(mu(3)-NH)(2)Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)](2)] (M = Mg, Ca, Sr, Ba). If 1 equiv of the group 2 amido reagent is employed, single-cube-type derivatives [(thf)(x)[(Me(3)Si)(2)N]M[(mu(3)-N)(mu(3)-NH)(2)Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)]] (M = Mg, x = 0; M = Ca, Sr, Ba, x = 1) can be isolated or identified. The tetrahydrofuran molecules are easily displaced with 4-tert-butylpyridine in toluene, affording the analogous complexes [(tBupy)[(Me(3)Si)(2)N]M[(mu(3)-N)(mu(3)-NH)(2)Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)]] (M = Ca, Sr). The X-ray crystal structures of [M(mu(3)-N)(mu(3)-NH)(5)[Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)](2)] (M = K, Rb, Cs) and [M[(mu(3)-N)(mu(3)-NH)(2)Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3))-N)](2)] (M = Ca, Sr) have been determined. The properties and solid-state structures of the azaheterometallocubane complexes bearing alkali and alkaline-earth metals are discussed.     

Polyurethanes crosslinked by metals and their complexes with crown ether

Two types of crosslinked polyurethanes (PU) have been synthesized: (a) PU crosslinked by metal ions (Cu²⁺ and Co²⁺), and (b) PU crosslinked by the complexes of metals with crown ether. Using X-ray scattering under small and wide angles the peculiarities of the structure of networks have been investigated. It was found that PU crosslinked by the metal crown ether complexes have a looser structure because of the bulky crosslink and diminished molecular mobility of the chains between two crosslinks, as was proven by the dielectric spectroscopy method. The X-ray and IR data have allowed proposing a scheme of the structure of the crosslinked PU with various types of crosslinks. The structures discovered may be considered as similar to metal catenandes. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1379–1386, 1998     

Use of polysulfides of alkali and alkaline-earth metals to obtain highly dispersed sulfur

Possibilities of obtaining polysulfides of alkali and alkaline-earth metals in aqueous solutions were considered. The composition of the polysulfides and their concentration in solutions were found. The efficiencies of application of highly dispersed sulfur, produced from calcium polysulfide, and colloid sulfur as a fungicide were compared.     

Studies of crown ether complexes aryldiazonium ion complexes

DNMR studies show that for complexation of aryldiazonium salts 21-crown-7 is the preferred host.     

Pulsed-field ionization electron spectroscopy and binding energies of alkali metal-dimethyl ether and -dimethoxyethane complexes

Lithium and sodium complexes of dimethyl ether (DME) and dimethoxyethane (DXE) were produced by reactions of laser-vaporized metal atoms with organic vapors in a pulsed nozzle cluster source. The mono-ligand complexes were studied by photoionization and pulsed field ionization zero electron kinetic energy (ZEKE) spectroscopy. Vibrationally resolved ZEKE spectra were obtained for Li(DME), Na(DME) and Li(DXE) and a photoionization efficiency spectrum for Na(DXE). The ZEKE spectra were analyzed by comparing with the spectra of other metal-ether complexes and with electronic structure calculations and spectral simulations. Major vibrations measured for the M(DME) (M=Li,Na) ions were M-O and C-O stretches and M-O-C and C-O-C bends. These vibrations and additional O-Li-O and O-C-C-O bends were observed for the Li(DXE) ion. The M(DME) complexes were in C2v symmetry with the metal atom binding to oxygen, whereas Li(DXE) was in a C2 ring configuration with the Li atom attaching to both oxygen atoms. Moreover, the ionization energies of these complexes were measured from the ZEKE or photoionization spectra and bond dissociation energies were derived from a thermodynamic cycle.     

Metalation of toluene and cumene with alkali metal-crown ether complexes

Metalation of toluene and isopropylbenzene with alkali metal-crown ether complexes led to the corresponding α-metalated alkylbenzenes. Treatment of the latter in succession with solid carbon dioxide, water, and hydrochloric acid gave carboxylic or dicarboxylic acids in 65–78% yield. Metalation of isopropylbenzene with sodium or potassium crown ether complexes above 90°C was accompanied by cleavage of the polyether ring with formation of organometallic compounds which then reacted with isopropylbenzene to produce 2-sodio(potassio)-2-phenylpropane and open-chain oligoether.     

Structure and stability of supramolecular crown ether complexes

Despite the fact that the complexation of ammonium cations with ionophores like crown ethers plays an important role in biological and industrial processes, there is still a lack of theoretical methods to reproduce or even predict the host–guest complex structures or their thermodynamic stabilities in an accurate manner. Hence, the development of ionophores has often relied on a trial‐and‐error approach and the synthetic efforts associated with this have been enormous, so far. Therefore, theoretical methods for the reliable prediction of binding affinities of crown ether derivatives with ammonium ions would be an indispensable tool for the rational design of new receptors with tailored properties. Here, we suggest a computationally efficient but still accurate theoretical approach. It is tested for a model system consisting of 18‐crown‐6 ether and an ammonium cation, but is invented for application to much larger complexes. The accuracy of various approximate quantum‐chemical methods, based on density functional theory (DFT) and many‐body perturbation theory, is evaluated against the gold standard CCSD(T) in the basis set limit as internal reference. An important aspect is the consideration of dispersion interactions in DFT methods, for which the dispersion‐correction by Grimme was employed. For all selected methods, the basis‐set dependence of calculated interaction energies was investigated. © 2015 Wiley Periodicals, Inc.     

Flaked capillary columns with crown ether complexes for gas-liquid chromatography

Flaked capillary columns with an OV-101/CE-Na{in3}PO{in4} hydrophobic-hydrophilic sorbent have been suggested. This sorbent provides for the analysis of polar and nonpolar substances, including amines and aminoalcohols, in aqueous and organic solvents. The efficiency of new columns was demonstrated for the analysis of 25 organic substances of various classes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2169–2173, December, 1994.The work was financially supported by the Russian Foundation for Basic Research, Project No. 93-03-4969.     

A fast atom bombardment mass spectrometric analysis of crown ether complexes [1]

Analyses of crown ether complexes of alkali metal ions and characterization of the complexes formed inm-nitrobenzyl alcohol have been carried out by fast atom bombardment (FAB) mass spectrometry. By using m-nitrobenzyl alcohol as a matrix for measurements, the stoichiometry of the complexes was assessed on the basis of the observed FAB peaks. In addition, the formation of crown ether-alkali metal complexes at a 2 : 1 molar ratio was enhanced by increasing the ionic radius of the metal ion in agreement with previous observations. On these grounds, FAB mass spectrometry may provide a rapid means for investigation of the complexation behavior of crown ethers and the stoichiometry of the complexes.     

Structural diversity of 1,2,4-diazaphospholide complexes with alkali metals

Treatment of H[3,5-Ph2dp] (Hdp = 1H-1,2,4-diazaphosphole) with nBuLi or KH, or the reaction of K[3,5-tBu2dp] with an excess amount of O2, afforded the dimeric species [(eta2,eta1-3,5-Ph2dp)Li(THF)2]2 and the polymeric complexes [(eta2:eta4-3,5-Ph2dp)K(Et2O2]n, and [[(eta2:eta5-3,5-tBu2dp)K(THF)][eta2(N,N)-eta3(O,P,O)-3,5-tBu2dp-(O,O)O2K]]n, respectively.     

Extraction of alkali metal picrates with poly- and bis(crown ether)s

Extraction of alkali metal picrates by new poly- and bis(crown ether)s containing benzo-15-crown-5 and benzo-18-crown-6 moieties was carried out with chloroform as water-immiscible solvent. The poly- and bis(crown ether)s were found to extract the picrates more effectively than the corresponding monocyclic crown ethers. In particular, poly- and bis(benzo-15-crown-5), and bis(benzo-18-crown-6) are remarkably effective extracting reagents for potassium and rubidium, and for caesium, respectively. Extraction equilibrium constants and the complexation constants in the chloroform phase were also evaluated and the contribution of the complexation constants to the extractability is discussed.     

Substituent effects on complexation and extraction of alkali metals with chromogenic crown ethers

The placing of chromogenic tags on crown ethers makes it possible to incorporate the natural selectivities of crown ethers into extractions with detection by visible spectrophotometry. The structures of these reagents include a monobasic amine linkage which, upon dissociation and complexation, gives a color change. The parent compound, 2″,4″,6″-trinitrophenyl-4'-aminobenzo-15-crown-5, provides a linear range for 10–800 ppm potassium ion in the presence of > 2000 ppm sodium ion. Changes in substituents on the chromophore (e.g., nitrile or trifluoromethyl for nitro) and the effects of these substituents on the visible spectra, extraction constants, equilibrium constants, the wavelength of maximum absorption, and the molar absorptivity are presented. Application of a compound to the determination of potassium ion in blood serum is reported.     

Superbulky metallocene complexes of the heavier alkaline-earth metals strontium and barium

Superbulky sandwich complexes with the cyclopentadienyl ligand (4-nBu-C(6)H(4))(5)Cp (abbreviated here as Cp(BIG)) have been prepared by reaction of Cp(BIG)H with benzylic strontium or barium reagents. Both metallocenes have been structurally characterized by single crystal X-ray diffraction. Even for the larger metallocene (Cp(BIG))(2)Ba a highly symmetric sandwich complex with parallel Cp rings was isolated (Cp(center)-Ba = 2.667(1) A). Both structures show evidence for a C-HC(pi) network between the Cp ligands. These attractive forces induce an inward out-of-plane bending of the aryl substituents (Sr 3.4(2) degrees ; Ba 5.3(2) degrees ). A linear correlation between this bending angle and metal size has been found.     

Molecular design of macrocyclic extractants for extraction and separation of alkali and alkaline-earth metals

The distribution coefficients of the alkaline and alkali-earth metal nitrates are determined for the processes of extraction from nitric acid solutions with crown ethers, which differ in sizes of their cycles (from 18 to 22 atoms) and in side phenyl and cyclohexyl substituents, but have unchanged number of the O atoms in a cycle. The phenyl and cyclohexyl derivatives of 18-crown-6 are found to be more efficient extractants of alkali metals as compared with unsubstituted crown ethers. However, the selectivity of separation of a pair Cs-Na remains low. The 18-crown-6 derivatives with one and two cyclohexyl fragments selectively extract Sr, which can be used to separate it from the remaining alkali and alkaline-earth metals. An increase in the size of a macrocycle from 18 to 20 and 22 atoms leads to a reduction in the extraction efficiency for all alkali and alkaline-earth metals, insignificantly improves separation of a pair Cs-Na, but noticeably deteriorates Sr-Na separation.