Positional Order and Disorder of Symmetric and Unsymmetric BEDT-STF Salts

The symmetric (s-) and unsymmetric (us-) BEDT-STF (=bis(ethylenedithio)diselenadithia-fulvalene) salts were prepared, and their crystal structures and electrical resistivities were investigated. Four us-BEDT-STF salts have the positional disorder of the Se atoms in the STF framework in crystals, whereas three s-BEDT-STF salts have no disorder. When κ-(us-BEDT-STF)₂GaCl₄ and κ-(cis-s-BEDT-STF)₂GaCl₄ are compared, the latter without the positional disorder of the Se atoms is more conductive than the former one with the disorder.     

Additive Effects of Lithium Salts with Various Anionic Species in Poly (Methyl Methacrylate)

We report that lithium salts in lithium-ion batteries effectively modify the physical properties of poly (methyl methacrylate) (PMMA). The glass transition temperature (T_g) is an indicator of the heat resistance of amorphous polymers. The anionic species of the salts strongly affected the glass transition behavior of PMMA. We focused on the additive effects of various lithium salts, such as LiCF₃SO₃, LiCOOCF₃, LiClO₄, and LiBr, on the T_g of PMMA. The large anions of the former three salts caused them to form macroscopic aggregates that acted as fillers in the PMMA matrix and to combine the PMMA domains, increasing T_g. On the other hand, LiBr salts dispersed microscopically in the PMMA matrix at the molecular scale, leading to the linking of the PMMA chains. Thus, the addition of LiBr to PMMA increased T_g as well as the relaxation time in the range of glass to rubber transition.     

Synthesis, crystal structure and thermal properties of [Co(NH3)5Cl]MO4 (M = Mo, W)

Crystal structures of [Co(NH₃)₅Cl]MoO₄ and [Co(NH₃)₅Cl]WO₄ complex salts are determined by single crystal X-ray diffraction. It is demonstrated for both salts that within the temperature range T = ?123?20°C there is a negative thermal expansion (about 0.26%) towards the c axis of the orthorhombic unit cell (Pnma space group). Thermal properties of the salts are investigated. The phase composition of the products obtained on heating the salts in different gas atmospheres is studied.     

The compressibility of molten salts

Values of the adiabatic and isothermal compressibility, κ_S and κ_T, of some 80 molten salts at the corresponding temperature of T = 1.1T_m (T_m is the melting point) are obtained from literature data either directly or re-calculated here. For some of the series of salts: alkali metal halides and nitrates, divalent metal halides, and alkali metal sulfates and carbonates the κ_T values are inversely proportional to the corresponding cohesive energy densities ced (internal energies per unit volume, separately for each class of compounds). The ced values for 1:2 and 2:1 salts not previously evaluated are presented here too.     

Thermal decomposition behavior of the rare-earth ammonium sulfate R2(SO4)3·(NH4)2SO4

Rare-earth ammonium sulfate octahydrates of R₂(SO₄)₃·(NH₄)₂SO₄·8H₂O (R=Pr, Nd, Sm, and Eu) were synthesized by a wet process, and the stable temperature region for the anhydrous R₂(SO₄)₃·(NH₄)₂SO₄ form was clarified by thermogravimetry/differential thermal analysis, infrared, Raman, and electrical conductivity measurements. Detailed characterization of these double salts demonstrated that the thermal stability of anhydrous R₂(SO₄)₃·(NH₄)₂SO₄ is different between the Pr, Nd salts and the Sm, Eu salts, and the thermal decomposition behavior of these salts was quite different from the previous reports.     

Spin solitons in organic charge-transfer salts

Organic charge-transfer (CT) salts that crystallize in face-to-face stacks of π-electron donors (D) and acceptors (A) are one-dimensional electronic systems with strong coupling to lattice and molecular vibrations. Peierls–Hubbard models of CT salts resemble π-electron theory of conjugated polymers, although transfer integrals t along mixed DA stacks are considerably smaller. Strong D and A yield Peierls systems with dimerized ground states of ion radicals, D⁺ and A⁻. Topological spin solitons separate regions of opposite dimerization, similarly to solitons in trans-polyacetylene, but are thermally accessible in ionic CT salts due to small t. Salts with still smaller t have Peierls transitions at T_P < 300 K to undimerized stacks. A Peierls–Hubbard model, H_CT, describes both types of salts and estimates of t are consistent with T_P < 300 K in some salts and spin solitons in others with higher T_P. Electron paramagnetic resonance (epr) spectra of single crystals provide direct evidence for spin solitons and one-dimensional electronic states. Spin solitons and H_CT resolve longstanding conflicts between vibrational and magnetic data that indicate dimerized stacks in several prototypical CT salts, while structural data point to undimerized stacks with large thermal ellipsoids. The low energy scale, availability of single crystals and diversity of CT salts offer opportunities for detailed modeling.     

Six- and seven-membered ring carbenes: Rational synthesis of amidinium salts, generation of carbenes, synthesis of Ag(I) and Cu(I) complexes

Reactions of neat 1,3- and 1,4-dibromides with N,N′-diarylformamidines in the presence of diisopropylethylamine (DIPEA) afford corresponding amidinium salts in high yields (>80%). Six- and seven-membered ring amidinium salts bearing bulky Mes (2,4,6-Me₃C₆H₂) and Dipp (2,6-ⁱPr₂C₆H₃) aryl groups were prepared using this method. Free six-membered ring carbene 6-Dipp was generated from amidinium salt using LiHMDS as a base. NHC-Ag(I) complexes were obtained by the reactions of amidinium salts with Ag₂O. NHC complexes of Pd and Rh are not accessible by deprotonation of amidinium salts, nor by transmetallation of Ag(I) complexes. However NHC-Cu(I) complexes were obtained by transmetallation of NHC-Ag(I). Thus, transmetallation of six- and seven-membered NHC-Ag(I) complexes was documented for the first time.     

N,N-Ethylene-bridged flavinium salts derived from l-valinol: synthesis and catalytic activity in H2O2 oxidations

Three chiral N¹,N¹⁰-ethylene-bridged flavinium salts with a stereogenic centre derived from l-valinol are prepared and investigated as oxidation catalysts. These salts efficiently catalyse chemoselective H₂O₂ oxidation of sulfides to sulfoxides and the oxidation of 3-phenylcyclobutanone to the corresponding lactone at room temperature. The flavinium salts react with hydrogen peroxide to form flavin-10a-hydroperoxide, which is the agent responsible for oxidation of the substrate.     

Electrospray mass spectrometry of borane salts: The electrospray needle as an electrochemical cell

Two borane salts ([(Me)₄N][B₃H₈] and Cs[B₃H₈]) were examined by electrospray mass spectrometry in the positive ion mode. Acetonitrile solutions provided the most informative spectra; the salts exhibited a remarkable degree of clustering under electrospray conditions, and virtually all signals corresponded to cationic cluster ions of the general formula {[cation ^m+] _x [anion ^n?] _y }^{(mx ? ny)+}. In contrast, methanol solutions of these salts produced only B(OCH₃) ₄ ^? cluster ions under otherwise identical conditions. ¹¹B NMR analyses corroborate the identities of the methanol solution species that enter the electrospray source and the reaction product generated during the electrospray process.     

Furan- and thiophene-functionalised bis-carbene ligands: Synthesis,silver(I) complexes,and catalysis

New furan- and thiophene-functionalised nucleophilic heterocyclic carbene (NHC) complexes of Ag(I) were prepared via the reaction of novel furan- and thiophene-functionalised bis-imidazolium salts with Ag₂O. Samples of both the N-methyl substituted furan- and thiophene-functionalised Ag(I) complexes suitable for single crystal X-ray studies were obtained following anion metathesis to the tetrafluoroborate salts. The structural characterisations revealed dinuclear [Ag₂(_MeCEC)₂](BF₄)₂ (E = O, S) formulations with discrete twenty-membered dimetallacycles present in both instances; however, the overall molecular conformation varies considerably, notably in the orientations of the two bridging furan or thiophene heterocycles to the silver coordination plane. The functionalised bis-imidazolium salts were tested as in situ additives in a Pd(0)-catalysed aryl amination coupling reaction, with the best observed activities around 20% of those seen with 1,3-bis(2,6-di-iso-propylphenyl)imidazolium chloride under identical conditions. The bulkier N-^tBu and N-mesityl substituted salts were found to be more active than the N-methyl substituted analogues.     

Thermal sensitivity of poly(N-vinylpyrrolidone) solutions in water-saline media

The effect of salts on the behavior of aqueous solutions of poly(N-vinylpyrrolidone), which is known to show no thermal sensitivity in the absence of additives, has been studied. The introduction of some salts, for example, KF, KH₂PO₄, K₂CO₃, and Na₂SO₄, leads to the occurrence of phase transitions. The corresponding phase transition temperatures depend on the nature and concentration of salts. Even moderate concentrations (0.3–0.6 mol/l) of the most active salts (K₂CO₃ and Na₂SO₄) are shown to reduce the phase transition temperature to 10–20°C.     

NMR spectroscopy study of 2-methylbenzoxazolium salts hydroxylation in DMSO-d6 solution

2-Methylbenzoxazolium salts showed an unexpected transformation at room temperature, promoted by residual water present in dimethyl sulfoxide. This transformation was followed up inside of an NMR sample tube using DMSO-d₆ as solvent, in a series of representative quaternary ammonium salts with carboxymethyl, ethyl, pentyl and decyl N-alkyl chains, resulting in an exclusive product. The corresponding benzothiazolium and benzoselenazolium salts presented a similar behavior after heating at a temperature of 50 °C with the addition of one drop of D₂O for the first of these two salts. This reaction could play a very important role in explaining certain secondary reactions occurring in the preparation of compounds where these salts are precursors, classically in cyanine dye synthesis. Four new benzoxazolols were characterized by NMR spectroscopy and HR FAB-MS.     

A simple access to metallic or onium bistrifluoromethanesulfonimide salts

Numerous salts of the (CF₃SO₂)₂N⁻ anion, called TFSI, were prepared according to an original one-pot procedure. First, N-benzyl trifluoromethanesulfonimide (N-benzyl triflimide) was treated with ethanol to form an oxonium intermediate, which was then neutralized by various bases to provide metallic or trialkylammonium triflimides salts. Alternatively, N-benzyl triflimide was directly treated with trialkyl sulfonium, quaternary ammonium or phosphonium halides to deliver the corresponding triflimide derivatives. N-Benzyl triflimide can be also reacted with di- or tri-alkylamines and phosphines to get benzyl onium salts. Analogous reactions can be carried out with N-allyl triflimide. Therefore, the TFSI anion can be very easily and expediently associated with a wide range of metallic or organic cations. Such salts can find applications as electrolytes for batteries and fuel cells, ionic liquids or Lewis acids.     

Synthesis of [M(NH3)5Cl](ReO4)2 (M = Cr, Co, Ru, Rh, Ir) and investigation of thermolysis products. Crystal structure of [Rh(NH3)5Cl](ReO4)2

Complex salts [M(NH₃)₅Cl](ReO₄)₂, where M = Cr, Co, Ru, Rh, Ir, have been prepared. The crystal structure of [Rh(NH₃)₅Cl](ReO₄)₂ was determined by single crystal X-ray diffraction. Crystal data: a = 17.369(4) Å, b = 7.7990(16) Å, c = 11.218(2) Å, V = 1430.5(5) ų, space group C2/m, Z = 4, d _calc = 3.19 g/cm³, R = 0.0447. Complex salts from the above series are shown to be isostructural; they were defined by X-ray crystallography. Thermal decomposition of the compounds in an inert atmosphere and under hydrogen has been studied. According to X-ray phase analysis (XRPA) data, the M_0.33Re_0.67 (M = Co, Ru, Rh, Ir) monophase solid solutions are the products of reduction of the salts under hydrogen.     

Tabulation of infrared spectral data : David Dolphin and Alexander E. Wick,John Wiley,New York,London, Sydney and Toronto, 1977, pp. xvi + 549, price £14.65

The infrared spectra of the isotopically isolated NH₃D⁺ and HDO species have been examined in seven ammonium Tutton salts. The observed spectra are in good agreement with predictions based on the known crystallographic features of these salts. Linear regression of the ND stretching frequencies v₁(NH₃D⁺) of the isotopically isolated NH₃D⁺ ion on hydrogen-bonded distance d(N ? O) indicated the existence of a correlation ; subsequent fitting of the data to a more plausible empirical function v₁(NH₃D⁺) = v_1,∞,-k₁ exp(-k₂,d) resulted in a coefficient of determination of 0.94 and a standard deviation of 10 cm^?1 for the goodness of fit. The structural differences caused by the distortion of the metal coordination octahedron in the copper(II) Tutton salts are discussed. For this purpose the spectra of isotopically dilute HDO in the salts M₂ⁱ[Cu(H₂O)₆](SO₄)₂ (Mⁱ = K, Rb, Cs) have also been measured. No evidence of phase transformations between room and liquid-nitrogen temperatures was detected in the spectra of any of the saltri studied in this work.     

Electron spin relaxation of new organic conductors: fluroranthenyl radical cation salts

Crystals of conducting fluoranthenyl (FA) radical cation salts (FA₂)⁺X^? with X^? = PF^?₆, AsF^?₆ show ESR linewidths (ΔH_pp) of ≈15 mOe at T = 293 K at microwave(9.5 GHz) and radio frequencies (230-60 MHz). ΔH_pp is independent of orientation. We analysed longitudinal and transverse relaxation and their dependence on temperature. These salts are suitable as magnetic field probes.     

Preparation des reactifs organolithiens a partir des acides ω-cyanocarboxyliques dans l'ammoniac liquide

By treating ω-cyanocarboxylic acids with lithium amide in liquid ammonia, salts, of the type [NCCH(CH₂)_nCOOLi]Li are prepared. The formation of these salts is confirmed by their reaction with N-benzolydiphenylketimine and benzophenone to give ω-diarlylate, ω-benzoylamino- and ω-hydroxy-ψ-cyanocarboxylic acids respectively.     

Polymerization of acrylamide in various solvents in the presence of Lewis acids

The radical polymerization of acrylamide in various solvents in the presence of Lewis acids has been investigated. Considerable effects of LiBr, LiCl and CaCl₂ on the total reaction rate and the values of k_p and k₁ for polymerization in DMSO or THF have been shown. For the polymerization of acrylamide in aqueous solution, addition of the salts does not affect the kinetic behaviour of the process. The observed effect of salts arises from complexation between the salt and the monomer and/or the propagating radicals.     

Reaction of closo-dodecaborate anion B12H 12 2− with iminium salts

The reaction of the closo-dodecaborate anion with iminium salts was studied. The iminium salts were either formed in situ or introduced into the reaction in an individual state. Mono-and disubstituted products with an exopolyhedral boron-nitrogen bond were found to form. The structures of compounds 1,7-[NMe₂(CH₂Cl)]₂B₁₂H₁₀ and 1,7-[MeNPh(CH₂Cl)]₂B₁₂H₁₀ were determined using X-ray crystallography.     

Thermodynamics of tetraalkyl- and bis- tetraalkylammonium bromides: II. Heat capacities of solid state from 273 to 373 K

The solid phase heat capacities of a number of hydrocarbon containing salts have been determined in the temperature range 273 to 373 K using a differential scanning calorimeter. The salts studied include tetramethyl-, tetraethyl-, and tetrabutylammonium bromide and the bis-tetraalkylammonium bromide series of the general formula [R₃N(CH₂)_nNR₃]Br₂, where n = 2,3… 10, and R = ethyl or allyl. With the exception of n-Bu₄NBr, the heat capacities of the salts were found to increase linearly with temperature over the range investigated. DSC curves of the bis-tetraalkylammonium series indicated that some of them have broad thermal transitions occurring between 365 K and their decomposition point, n-Bu₄NBr was the only tetraalkylammonium salt to show any anomalous thermal transitions in the solid phase. The origin of these transitions may be due to mesophase formation.