Dodecahydroxy-closo-dodecaborate(2-).

The cesium salt of the icosahedral borane anion dodecahydroxy-closo-dodecaborate(2-), Cs(2)[closo-B(12)(OH)(12)], Cs(2)1, was prepared by heating cesium dodecahydro-closo-dodecaborate(2-), Cs(2)[closo-B(12)H(12)], Cs(2)2, with 30% hydrogen peroxide. The other alkali metal salts A(2)1 (A = Li, Na, K, Rb) precipitated upon addition of ACl to warm aqueous solutions of Cs(2)1. The ammonium salt, [NH(4)](2)1, and the (mu-nitrido)bis(triphenylphosphonium) salt, [PPN](2)1, were obtained similarly. The [H(3)O](2)1 salt precipitated upon acidification of aqueous solutions of Cs(2)1 with hydrochloric acid. The solubility of these salts in water was determined by measuring the boron content of saturated aqueous solutions of A(2)1 (A = Li, Na, K, Rb, Cs), [H(3)O](2)1, and [NH(4)](2)1 using ICP-AES. Although these salts are derived from a dianion with twelve pendant hydroxyl groups, the alkali metal salts surprisingly displayed low water solubilities. Water solubility decreases with a decrease in the radius of A(+), except for the lithium salt, which is slightly more soluble than the potassium salt. The [H(3)O](2)1 and the [NH(4)](2)1 salts provide rare examples of water-insoluble hydronium and ammonium salts. The low water solubility of the A(2)1 salts is attributed to the dianion's pendant hydroxyl groups, which appear to function as cross-linking ligands. Four alkali metal salts, A(2)1 (A = Na, K, Rb, Cs), were characterized in the solid state by single-crystal X-ray crystallography. These data revealed intricate networks in which several anions are complexed through their hydroxyl groups to each alkali metal cation. In addition, the anions are engaged in hydrogen bonding with each other and, if present, with water of hydration. This cross-linking results in the precipitation of aggregated salts. Cation coordination numbers decrease with cation radius. Thus, cesium and rubidium are ten-coordinate, whereas potassium is seven-coordinate and sodium is six-coordinate. The geometry of anion 1(2)(-) is independent of cation identity; the B-B and B-O bond lengths of the various A(2)1 salts (A = Na, K, Rb, Cs) are identical.     

Compounds of Alkali Metal Anions

Anions of sodium, potassium, rubidium, and cesium are stable both in suitable solvents and in crystalline solids. The latter can be prepared either by cooling a saturated solution or by rapid solvent evaporation. Thermodynamic arguments show that alkali metal anions can probably exist in saturated solutions of the alkali metals in any compatible solvent, but that below saturation, dissociation into the cation and solvated electrons is favored in highly polar solvents such as ammonia. The key to solvent-free salts of the alkali metal anions is stabilization of the cation by incorporation into a suitable crown or cryptand complex. By using such complexes it also appears possible to produce “electride” salts in which the charge of the complexed cation is balanced by a trapped electron. The chemical, electrical, and optical properties of salts of the alkali metal anions and “electrides” could provide useful applications.     

Synthesis and some Reactions of Alkali Metal Carbamotelluroates

Sodium and potassium carbamotelluroates [M(R₂NCOTe), M = Na, K, Rb, Cs] were synthesized in moderate to good yields by reacting carbamoyl chloride with the corresponding alkali metal tellurides. The salts readily reacted with trimethylsilyl chloride to form O‐trimethylsilyl carbamotelluroate (R₂NCTeOSiMe₃), which further reacted with RbF and CsF to lead to the corresponding heavy alkali metal carbamotelluroates. These salts reacted with alkyl iodide and carbamoyl chlorides to give the corresponding Te‐alkyl carbamotelluroates and dicarbamoyl tellurides in moderate yields.     

Sodium and potassium benzeneazophosphonate complexes with crown ethers: Solid-state microwave synthesis, characterization and biological activity

The eco-friendly synthesis, spectroscopic (IR, MS, ¹H and ¹³C NMR) study and biological (cytostatic, antiviral) activity of sodium and potassium benzeneazophosphonate complexes, obtained by reaction in the solid state under microwave irradiation of the alkali salts of ethyl [α-(4-benzeneazoanilino)-N-benzyl]phosphonic acid and [α-(4-benzeneazoanilino)-N-4-methoxybenzyl]phosphonic acid with crown ethers containing 18-membered (dibenzo-18-crown-6 and bis(4′-di-tert-butylbenzo)-18-crown-6), 24-membered (dibenzo-24-crown-8) and 30-membered (dibenzo-30-crown-10) macrocyclic rings, have been described. The simple work-up solvent free reaction is an efficient green procedure for the formation of mononuclear crown ether complexes in which the sodium/potassium ion is bound to oxygen atoms of the macrocycle and the phosphonic acid oxygen. The free crown ethers, alkali benzeneazophosphonate salts and their complexes were evaluated for their cytostatic activity in vitro against murine leukemia L1210, murine mammary carcinoma FM3A and human T-lymphocyte CEM and MT-4 cell lines, as well as for their antiviral activity against a wide variety of DNA and RNA viruses. The investigated compounds showed no specific antiviral activity, whereas all the free crown ethers and their complexes demonstrated cytostatic activity, which was especially pronounced in the case of bis(4′-di-tert-butylbenzo)-18-crown-6 and its complexes.     

Fast atom bombardment mass spectrometry of alkali metal fluorides and chlorides; a comparison of the solid salt and glycerol matrix spectra

The Fast Atom Bombardment (FAB) mass spectra of the alkali metal chlorides (Na, K, Cs) and fluorides (Na, K, Rb, Cs) were obtained from solids and a glycerol matrix, using a fast atom bombardment source. From solids the fluorides exhibited an ion abundance enhancement of the well-known [M(MF)₄]⁺ cluster, which decreased with increasing cation size. A gradual decrease in the n=4 enhancement was observed as the salt was diluted with glycerol. In the chlorides only sodium chloride showed the n=4 relative enhancement. The mass spectra of the salts from a glycerol matrix at molar ratios of 1:1 to 1:10 showed that the spectra of the 1:1 solutions were similar to those from the solids, while glycerol adducts were found to increase with increasing glycerol concentration. A [M(MX)_n(gly)]⁺ species that featured successive losses of HX was observed. It has not been established whether HX losses take place in solution, in the surface/vacuum interface and/or whether gas phase reactions might be responsible for the observation of the [M(MX)_n(gly)–y HX]^? species in the mass spectra of the MX/glycerol system.     

肉豆蔻酸和棕榈酸酸盐体系的振动光谱研究

报道了肉豆蔻酸和榈酸酸盐体系的振动光谱，结果表明，脂肪酸与其碱金属盐之间通过氢键和羧基配位形成酸盐络合物。酸盐体系中氢键具有不同于普通氢键的性质，本文结合振动光谱讨论了酸盐的结构和氢键性质。     

Synthesis,structures, and conformational characteristics of calixarene monoanions and dianions

The synthesis, complete characterization, and solid state structural and solution conformation determination of calix[n]arenes (n = 4, 6, 8) is reported. A complete series of X-ray structures of the alkali metal salts of calix[4]arene (HC4) illustrate the great influence of the alkali metal ion on the solid state structure of calixanions (e.g., the Li salt of monoanionic HC4 is a monomer; the Na salt of monoanionic HC4 forms a dimer; and the K, Rb, and Cs salts exist in polymeric forms). Solution NMR spectra of alkali metal salts of monoanionic calix[4]arenes indicate that they have the cone conformation in solution. Variable-temperature NMR spectra of salts HC4.M (M = Li, Na, K, Rb, Cs) show that they possess similar coalescence temperatures, all higher than that of HC4. Due to steric hindrance from tert-butyl groups in the para position of p-tert-butylcalix[4]arene (Bu(t)C4), the alkali metal salts of monoanionic Bu(t)C4 exist in monomeric or dimeric form in the solid state. Calix[6]arene (HC6) and p-tert-butylcalix[6]arene (Bu(t)C6) were treated with a 2:1 molar ratio of M(2)CO(3) (M = K, Rb, Cs) or a 1:1 molar ratio of MOC(CH(3))(3) (M = Li, Na) to give calix[6]arene monoanions, but calix[6]arenes react in a 1:1 molar ratio with M(2)CO(3) (M = K, Rb, Cs) to afford calix[6]arene dianions. Calix[8]arene (HC8) and p-tert-butylcalix[8]arene (Bu(t)()C8) have similar reactivity. The alkali metal salts of monoanionic calix[6]arenes are more conformationally flexible than the alkali metal salts of dianionic calix[6]arenes, which has been shown by their solution NMR spectra. X-ray crystal structures of HC6.Li and HC6.Cs indicate that the size of the alkali metal has some influence on the conformation of calixanions; for example, HC6.Li has a cone-like conformation, and HC6.Cs has a 1,2,3-alternate conformation. The calix[6]arene dianions show roughly the same structural architecture, and the salts tend to form polymeric chains. For most calixarene salts cation-pi arene interactions were observed.     

A Bulky m‐Terphenyl Cyclopentadienyl Ligand and Its Alkali‐Metal Complexes

The synthesis of the new m ‐terphenyl‐substituted cyclopentadienyl ligand precursor 1‐cyclopentadiene‐2,6‐bis(2,4,6‐trimethylphenyl)benzene (Ter^MesCpH) is described. The synthesis proceeds through the reaction of Ter^MesLi with cobaltocenium iodide, followed by oxidation of the intermediate cobalt(I) species to give the corresponding cyclopentadiene as a mixture of isomers. The preparation and spectroscopic properties of the alkali‐metal salts (Li–Cs) is described, as well as structural information obtained by X‐ray diffraction studies for the lithium, potassium, and cesium analogues. Crystallographic data demonstrate the ability of these new ligands to act as monoanionic chelates by forming metal complexes with Cp–M–Ar bonding environments.     

Gas phase hydrogen deuterium exchange reactions of a model peptide: FT-ICR and computational analyses of metal induced conformational mutations

We utilized gas phase hydrogen/deuterium (H/D) exchange reactions and ab initio calculations to investigate the complexation between a model peptide (Arg-Gly-AspRGD) with various alkali metal ions. The peptide conformation is drastically altered upon alkali metal ion complexation. The associated conformational changes depend on both the number and type of complexing alkali metal ions. Sodium has a smaller ionic diameter and prefers a multidentate interaction that involves all three amino acids of the peptide. Conversely, potassium and cesium form different types of complexes with the RGD. The [RGD + 2Cs − H]⁺ species exhibit the slowest H/D exchange reactivity (reaction rate constant of 6 × 10⁻¹³ cm³molecule⁻¹s⁻¹ for the fastest exchanging labile hydrogen with ND₃). The reaction rate constant of the protonated RGD is two orders of magnitude faster than that of the [RGD + 2Cs − H]⁺. Addition of the first cesium to the RGD reduces the H/D exchange reaction rate constant (i.e., D₀) by a factor of seven whereas sodium reduces this value by a factor of thirty. Conversely, addition of the second alkali metal ions has the opposite effect; the rate of D₀ disappearance for all [RGD + 2Met − H]⁺ species (MetNa, K, and Cs) decreases with the alkali metal ion size.     

Identification of flame retarding organic alkali metal salt additives in polycarbonate by flow injection electrospray ion trap mass spectrometry

Three commonly used flame retarding organic alkali metal salt additives in polycarbonate, potassium diphenylsulfone sulfonate, potassium perfluorobutane sulfonate and p-toluenesulfonic acid sodium salt could be simultaneously, quickly and conveniently identified in a polycarbonate sample by utilizing electrospray ion trap mass spectroscopy detection in flow injection mode after dissolution and precipitation of the polymer. The resulting method offered advantages of speed, selectivity and precision of identification based on two stage mass spectroscopy fragmentation patterns and mass spectral library matching for the three salts tested, and is likely to be applicable to other compounds of similar class.     

Improved matrix-assisted laser desorption/ionization mass spectrometric detection of glycosaminoglycan disaccharides as cesium salts

Ultraviolet matrix-assisted laser desorption/ionization mass spectrometric (UV-MALDI-MS) analysis of highly acidic, thermally labile species such as glycosaminoglycan-derived oligosaccharides is complicated by their poor ionization efficiency and tendency to fragment through the loss of sulfo groups. We have utilized a systematic approach to evaluate the effect of alkali metal counterions on the degree of fragmentation through SO3 loss from a highly sulfated model compound, sucrose octasulfate (SOS). The lithium, sodium, potassium, rubidium, and cesium salts of SOS were analyzed by UV-MALDI-time-of-flight (TOF)MS using an ionic liquid matrix, bis-1,1,3,3-tetramethylguanidinium alpha-cyano-4-hydroxycinnamate. The positive-ion and negative-ion MALDI mass spectra of five alkali metal salts of SOS were compared in terms of the degree of analyte fragmentation through the SO3 loss and the absolute intensity of a molecular ion signal. Experimental results demonstrate that the lithium, sodium, and potassium salts of SOS undergo some degree of fragmentation through the loss of SO3, whereas the fragmentation through the loss of SO3 in the rubidium and cesium salts of SOS is suppressed. A high detection sensitivity associated with the stability of sulfate half-esters was achieved for the cesium salt of SOS using positive-ion detection. Finally, the cesium salt of chondroitin sulfate A disaccharide was successfully analyzed using UV-MALDI-TOFMS.     

Elaboration of a chiral 20-crown-6 from a glucofuranose derivative and its complex formation with alkali cations

The synthesis of bis-(1,2-O-isopropylidene-6-O-triphenylmethyl-α-D-glucofuranosyl)-20-crown-6 ( 1 ) and its complexing ability with alkali and ammonium cations are described. The crown ether 1 was synthesized in a stepwise manner via the “half-crown” ( 2 ) using a blocking-deblocking procedure, in which the 3,3′-bridge was formed, followed after suitable manipulations, by formation of the 5,5′-bridge. An unusual feature of the complexing ability of the crown ether is that, although potassium and ammonium ions most closely approach the size of the complexing cavity, it is the sodium ion which forms the most stable complex. Compound 1 does not show chiral recognition toward two alkylammonium salts.     

Preparation of high purity alkali metals by near melting point segregation

Pure alkali metal preparation is a complex problem: in most available commercial samples, all of them are simultaneously present. Conventional separation techniques are not always effective enough to reach parts per million total impurity levels. However, near the melting point, superficial segregation occurs. A zone melting derived technique coupled with a specifically developed solvent extraction process allows the total impurity content of sodium to be lowered below a few parts per million. The described thermal process, although using chemical reactions, is purely physically steered: it purifies as well potassium containing sodium as sodium containing potassium. 4 alkali metals are considered: Li, Na; K, and Cs.     

Conductance behavior of electrolytes in 1,3-dimethylethyleneurea and 1,3-dimethylpropyleneurea at 25°C

1,3-Dimethylethyleneurea (DMEU) and 1,3-dimethylpropyleneurea (DMPU) were investigated as electrolytic media for a number of alkali metal and triisoamylbutylammonium salts via conductivity measurements over a concentration range of 1–100×10^–4 M at 25°C. The data were analyzed by the Fuoss-Shedlovsky, Fuoss-Onsager, and expanded Pitts equations. The limiting equivalent conductivities were about 1.5 times greater in DMEU than in DMPU, which is exactly the ratio of the viscosities. From the Fuoss-Onsager analysis, all salts studied were found to be essentially unassociated in both solvents. From the expanded Pitts equation the extent of association was small, but within a salt series the equation indicated that association decreased in the order iodides, thiocyanates > perchlorate > tetraphenylborates. Neither solvent differentiated between sodium and potassium ion mobilities, indicating a type of solvation behavior different from that in acyclic urea solvents such as tetramethyl- and tetraethylurea.     

Urchin-Type Architecture Assembled by Cobalt Phosphide Nanorods Encapsulated in Graphene Framework as an Advanced Anode for Alkali Metal Ion Batteries

Urchin-type cobalt phosphide microparticles assembled by nanorod were encapsulated in a graphene framework membrane (CoP@GF), and used as a binder-free electrode for alkali metal ion batteries. Electrochemical measurements indicate that this membrane exhibits enhanced reversible lithium, sodium, and potassium storage capabilities. Moreover, the energy storage properties of CoP@GF electrodes in alkali metal ion batteries display an order of Li>Na>K. DFT calculations on adsorption energy of CoP surfaces for Li, Na, and K indicated that CoP surfaces were more favorable to transfer electrons to Li atoms than Na and K, and the surface reactivity can be ordered as Li-CoP>Na-CoP>K-CoP; thus, CoP@GF exhibits better storage capacity for lithium. This work provides experimental and theoretical basis for understanding the electrochemical performance of cobalt phosphide-based membranes for alkali metal ion batteries.     

Solid-state Structures and Solution Behavior of Alkali Salts of the [\hbox{Nb}_{6}\hbox{O}_{19}]^{8-} Lindqvist Ion

The hexaniobate Lindqvist ion has long been known as the dominant specie in alkaline niobium oxide solutions. Recent advances in heteropolyniobate chemistry continue to be greatly aided by use of alkali salts as soluble precursors; in particular, potassium, sodium and lithium hexaniobate salts. We report here the solid-state characterization and solution behavior of Li, K, Rb and Cs Lindqvist salts. Synthesis and single-crystal X-ray diffraction data is reported for nine new hexaniobate salts. These structures differ in the number of charge-balancing alkali cations, protonation of the clusters, relative arrangement of the clusters and alkali metal cations, amount of lattice water and its mode of interaction with other lattice species. Trends of alkali-cluster bonding are observed as a function of alkali radius. Protonation of the clusters in the solid-state is influenced by the method of crystallization of the salt. Lability of the cluster oxygens is observed by solution ¹⁷O NMR experiments. Rates of isotopic enrichment of the bridging oxygen, terminal oxygen and bridging hydroxyl cluster sites are compared for aqueous solutions of Li, K, Rb and Cs hexaniobate salts. Parameters influencing the oxo-ligand exchange rates of the salts are discussed relative to their use as heteropolyniobate precursors.This paper is dedicated to Professor Michael T. Pope on the event of his retirement to acknowledge his fruitful career in polyoxometalate chemistry.     

Laser desorption fourier transform mass spectra of ascorbic and isoascorbic acids

Positive and negative ion laser desorption Fourier transform mass spectra of ascorbic acid, isoascorbic acid, and their sodium and potassium salts have been determined. A number of differences between these spectra and previously reported laser microprobe mass analyzer (LAMMA) spectra are found. In contrast with earlier results, m/z 175 anions are present in all negative ion spectra, as are cluster ions. Thus, it should not be concluded that the radical salts are electroneutral, as claimed in the earlier study.     

Ab Initio Calculation of the Structure and Functions of Sulfo Cation Exchangers

An ab initio calculation has been carried out for hydrated lithium, sodium, potassium, and rubidium toluenesulfonates, modeling the structure of sulfo cation exchangers in the form of alkali metal ions. In the optimized structure, water molecules are incorporated between the fixed ion and the counterions. This leads to dissociation of the ionogen groups, which increases the diffusion mobility of the counterions. Analysis of an elementary ion exchange process has revealed that cleavage of hydrogen bonds between the hydration water molecules of the fixed ion and the counterions plays a critical role in the ion exchange mechanism.     

NMR studies of interionic interactions in N-methylformamide

The NMR chemical shifts of alkali and thallium(I) salts with various monovalent anions have been measured in N-methylformamide solution. Lithium-7 chemical shifts are virtually concentration and counter-ion independent, presumably due to an absence of direct cation-anion interactions. The sodium-23, potassium-39 and cesium-133 chemical shifts of the salts studied depend on the anion and vary linearly with the concentration. The observed behavior can be accounted for by the formation of collisional ion pairs. On the other hand, the thallium-205 chemical shifts of thallium(I) nitrate and perchlorate were anion-dependent and varied non-linearly with the salt concentration. These results are indicative of contact ion pair formation; formation constants were calculated to be 2.6±0.4 M ^–1 for TlNO ₃ and 1.7±0.5 M ^–1 for TlClO ₄ . The cesium-133 NMR spectra of several mixed electrolyte systems also have been measured in N-methylformamide solution. The¹³³Cs chemical shifts also change linearly with the concentrations of the salts added to 0.10 M CsI/NMF solutions. The influence of the anions on the chemical shifts is the same as that observed for cesium salts alone.     

Identification of isothiocyanates (Mustard oils) and liquid primary amines via the formation of 1-substituted 2-tetrazoline-5-thione

The oscillometric method is suggested for the determination of alkali salts of organic acids in non-aqueous media. In the titrations of organic sodium and potassium salts the influence of water content and dielectric constant of non-aqueous solvents on the slopes of the titration curves was investigated. Errors obtained were in the range of±0.6 to 1.5%.