Discussion on the formation and bonding in three [Ga8R10] compounds: the diversity in classical Ga-Ga bonds

Herein we describe three Ga(8) compounds that feature gallium atoms in an oxidation state of 1.25 with normal valent 2e-2c bonding. Their structures and the influence of their ligands (phosphorus and nitrogen atoms directly bonded to the Ga(8) moieties) are discussed on the basis of DFT calculations, providing an insight into a probable mechanism for insertion reactions between GaX and GaX(3) species that lead to a reaction cascade via halides like Ga(2)X(4) and Ga(5)X(7) to Ga(8)X(10) and Ga(8)X(12) (2-), respectively. Finally, the Ga(8) cores of the three title compounds were compared with the topology of carbon atoms in C(8) alkanes.     

Synthesis and characterization of stable hypervalent carbon compounds (10-C-5) bearing a 2,6-bis(p-substituted phenyloxymethyl)benzene ligand

X-ray analysis of bis(p-fluorophenyl)methyl cation bearing a 2,6-bis(p-tolyloxymethyl)benzene ligand showed a symmetrical structure (10-C-5) where the two C-O distances are identical, although the distance (2.690(4) A) is longer than those (2.43(1) and 2.45(1) A) of 1,8-dimethoxy-9-dimethoxymethylanthracene monocation, which was recently reported by us. However, X-ray analysis of the more stable aromatic xanthylium cation with the same benzene ligand showed the tetracoordinate carbon structure where only one of the two oxygen ligands is coordinated with the central carbon atom. These results clearly indicate that the carbocations (10-C-5) bearing the sterically flexible benzene ligand were quite sensitive to the electronic effect on the central carbon atom. The electron distribution analysis by accurate X-ray measurements and the density functional calculation on the initially mentioned bis(p-fluorophenyl)methyl cation clearly show that the central carbon atom and the two oxygen atoms are bonded even if the bond is weak and ionic based on the small value of the electron density (rho(r)) and the small positive Laplacian value (nabla(2)rho(r)) at the bond critical points.     

Reaction of alkynyltrimethylsilanes with a hypervalent organoiodine compound: A new general synthesis of alkynyliodonium salts

New general methods for the synthesis of alkynyl(phenyl)iodonium tetrafluoroborate 2 from alkynyltrimethylsilanes 1 utilizing the combination of iodosylbenzene and triethyloxonium tetrafluoroborate or boron trifluoride etherate were developed. The medium effect observed in the reaction was also discussed.     

First isolation and kinetic study of hypervalent 10-As-5 organoarsenic compounds with a C-apical, O-equatorial configuration

Hypervalent organoarsenic compounds violating the apicophilicity concept were isolated for the first time, and the energy of isomerization of these arsoranes to the more stable stereoisomers appeared to be lower than that of the phosphorus analogues based on the kinetic studies.     

Water-soluble pillar[5]arenes: A new class of plant growth regulators

It is highly valuable to develop bifunctional chemical fertilizers that can both regulate plant growth and reduce the toxicity of pesticides. Here we report three water-soluble pillar[5]arenes WP5-1, WP5-2 and WP5-3 established as efficient plant growth regulators for wheat to efficiently improve the development of buds and roots in the seedling cultivation stage. Moreover, as macrocyclic hosts for the poisoning herbicide paraquat, WP5-2 and WP5-3 can also be employed to reduce its toxicity based on host–guest interactions, as confirmed by cell viability experiments towards HEK 293 and Raw 264.4 cell lines.     

1,2,5]Thiadiazolo[3,4-c][1,2,5]thiadiazolidyl: a long-lived radical anion and its stable salts

[1,2,5]Thiadiazolo[3,4-c][1,2,5]thiadiazole (1) is synthesized in 62% yield by fluoride ion-induced condensation of 3,4-difluoro-1,2,5-thiadiazole with (Me(3)SiN=)(2)S. The reversible electrochemical reduction of 1 leads to the long-lived [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazolidyl radical anion (2) and further to the dianion (3). The radical anion 2 is also obtained by the chemical reduction of the precursor 1 with t-BuOK in MeCN. The radical anion 2 is characterized by ESR spectroscopy in solution and in the crystalline state. The stable salts [K(18-crown-6)][2] and [K(18-crown-6)][2].MeCN (8 and 9, respectively) are isolated from the spontaneous decomposition of the [K(18-crown-6)][PhXNSN] (6, X = S; 7, X = Se) salts in MeCN solution followed by XRD characterization. The radical anion 2 acts as a bridging ligand in 8 and as chelating ligand in 9. The structural changes observed by XRD in going from 1 to 2 are explained by means of DFT/(U)B3LYP/6-311+G calculations.     

Geminal imidazolium salts: a new class of gelators

The gelling behavior of some geminal diimidazolium salts was investigated in solvents differing in polarity and hydrogen bond donor ability. The used salts, namely the 3,3'-di-n-decyl-1,1'(1,4-phenylenedimethylene)diimidazolium dibromide [p-Xyl-(decim)(2)][Br](2) (1), the 3,3'-di-n-dodecyl-1,1'(1,4-phenylenedimethylene)diimidazolium dibromide [p-Xyl-(dodecim)(2)][Br](2) (2), and the 3,3'-di-n-dodecyl-1,1'(1,4-phenylenedimethylene)diimidazolium ditetrafluoroborate [p-Xyl-(dodecim)(2)][BF(4)](2) (3), differ in the alkyl chain length and in the anion properties, such as size, shape, and coordination ability. In all cases in which gelation process was observed, the obtained gels were characterized by gel melting temperature determination, resonance light scattering, and UV-vis measurements. On the whole, the investigation allowed to get information about both the thermodynamic stability and the features of the aggregates characterizing the soft materials at the equilibrium. Data collected by us point out that the used organic salts are able to behave as both hydro- and organogelators. In particular, bromide salts formed hydrogels in the presence of α-cyclodextrin allowing to hypothesize that the gelation process is favored by the formation of supramolecular assemblies. To verify this hypothesis, 1D and 2D (1)H NMR measurements were carried out. Both the alkyl chain length and the anion ability to reticulate the three-dimensional network proved to be determinant factors in affecting the gelation process as well as the features of the gel phases. Finally, with the future aim to use the obtained gels as reaction media, the effect of a guest molecule such as the UV-vis active probe Nile Red was studied.     

Calix[4]tubes: a new class of potassium-selective ionophore

A new class of cryptand-like ionophore based on a bis calix[4]arene structure has been developed. These molecules proved highly selective for complexation of potassium over all group I metal cations and barium. A range of symmetric and asymmetric calix[4]tubes featuring either alkyl or phenyl substituents at the upper rim have been synthesized in exceptional yield. Alteration of the calix[4]arene upper rim environment enables fine-tuning of the rate of potassium uptake, which can be evaluated through the conformational change on binding by NMR studies. Selectivity of potassium complexation has been demonstrated using NMR and electrospray mass spectral techniques. Molecular modeling studies, derived from crystallographic data, confirm that the potassium metal cation is complexed via the axial route, passing through the calix[4]arene annulus, and provide evidence for complexation rate and selectivity.     

Synthesis of derivatives of pyrazolo[1,5-a]pyrrolo[1,2-c][1,3,6]-benzotriazocine,a new class of compounds with potential CNS activity

The synthesis of derivatives of pyrazolo[1,5-a]pyrrolo[1,2-c][1,3,6]benzotriazocine was obtained by the reaction of arylaldehydes with some 1-(2-aminophenyl)-5-(pyrrol-1-yl)pyrazoles, as hydrochlorides. Characterization of this new class of compounds was effected with ir, pmr and ¹³C nmr spectral data.     

Two new cluster ions, Ga[GaH3]4(5-) with a neopentane structure in Rb8Ga5H15 and [GaH2]n(n-) with a polyethylene structure in Rb(n)(GaH2)n, represent a new class of compounds with direct Ga-Ga bonds mimicking common hydrocarbons

The first examples of a new class of gallium hydride clusters with direct Ga-Ga bonds and common hydrocarbon structures are reported. Neutron powder diffraction was used to find a Ga[GaH(3)](4)(5-) cluster ion with a neopentane structure in a novel cubic structure type of Rb(8)Ga(5)H(15). Another cluster ion with a polyethylene structure, [GaH(2)](n)(n-), was found in a second novel (RbGaH(2))(n) hydride. These hydrocarbon-like clusters in gallium hydride materials have significant implications for the discovery of hydrides for hydrogen storage as well as for interesting electronic properties.     

A new class of bicyclic dicationic salts based on the 7-azoniabicyclo[2.2.1]heptane scaffold

A new class of dicationic ionic salts has been developed based on two 7-azoniabicyclo[2.2.1]heptane moieties and a variable spacer. The construction of the 7-azabicyclo[2.2.1]heptane skeleton and introduction of the two- to ten-atom spacer occurred concurrently in a one-pot reaction. Quaternization and subsequent metathesis afforded the dicationic salts consisting of two linked quaternized bicyclic moieties and bis(trifluoromethylsulfonyl)imide or dicyanamide as counterions. These salts are liquids at room temperature if the spacer length was larger than seven atoms. X-ray diffraction analysis revealed a linear conformation of the spacer and RS/SR stereochemistry of the quaternized nitrogens.     

Complexes of triethanolamine with aroxyacetic acids and their metal salts as a new class of biologically active compounds

A series of complexes of triethanolamine with metal salts of aroxyacetic acids has been prepared. The complexes are perspective biologically active compounds for search for new immunomodulating, antistress, anti-inflammatory and other types of agents. The structure and acid-base properties of these compounds were studied by NMR and IR spectroscopy and potentiometric titration.     

Chiral quaternary phosphonium salts: a new class of organocatalysts

Phase-transfer catalysis has widely been used as a prime synthetic tool for both laboratory and industrial processes. During the last twenty years, asymmetric phase-transfer catalysis using chiral organocatalysts has attracted widespread interest. However, the scope of chiral phase-transfer catalysis has been limited mostly to the quaternary ammonium salts. As an emerging area, the recent developments in the application of quaternary phosphonium salts as chiral phase-transfer catalysts are discussed in this article.     

Cs[Cl3F10]: A Propeller‐Shaped [Cl3F10]− Anion in a Peculiar A[5]B[5] Structure Type

Reaction of CsF with ClF₃ leads to Cs[Cl₃F₁₀]. It contains a molecular, propeller‐shaped [Cl₃F₁₀]^? anion with a central μ₃‐F atom and three T‐shaped ClF₃ molecules coordinated to it. This anion represents the first example of a heteropolyhalide anion of higher ClF₃ content than [ClF₄]^? and is the first Cl‐containing interhalogen species with a μ‐bridging F atom. The chemical bonds to the central μ₃‐F atom are highly ionic and quite weak as the bond lengths within the coordinating XF₃ units (X = Cl, and also calculated for Br, I) are almost unchanged in comparison to free XF₃ molecules. Cs[Cl₃F₁₀] crystallizes in a very rarely observed A^[5]B^[5] structure type, where cations and anions are each pseudohexagonally close packed, and reside, each with coordination number five, in the trigonal bipyramidal voids of the other.     

Synthesis and characterization of a new pillar[5]arene-based [1]rotaxane

In this study, we reported the synthesis of three kinds of mono-functional pillar[5]arene derivatives PRI, PRII and R and their structures were studied by 1D and 2D NMR spectra and mass spectra. The 2D NMR spectra including ¹H-¹³C HSQC, ¹H-¹H COSY and NOESY spectra indicated that PRI and PRII are both stable self-included pseudo[1]rotaxanes in CDCl₃. These original structures are promising compounds for the design of pillar[5]-based [1]rotaxane. And the results showed that R could exist stable in CDCl₃ and DMSO because of the coordination of N-H?O hydrogen bonding interaction and C-H?π interaction.     

Synthesis of a new calix[n]pyrrole: meso-pentaspirocyclohexyl calix[5]pyrrole

We describe the first synthesis of the novel meso-pentaspirocyclohexyl calix[5]pyrrole 2b. Anion-guest properties of the new compound were evaluated with respect to fluoride, chloride, and bromide tetrabutylammonium salts by ¹H NMR titration techniques in deuterated dichloromethane at 22 °C by following the induced shifts in the NH resonances upon complexation.     

Interaction of benzothieno[2,3-c]pyrylium salts with hydrazine. Derivatives of 5H-[2,3]benzothieno[2,3-e]diazepines

A study has been made of the reaction of 1,3-disubstituted bezothieno[2,3-c]pyrylium salts with hydrazine. It has been shown that 1,3-dialkyl-substituted benzothieno[2,3-c]pyrylium salts interact with hydrazine to give N-amino-1,3-dialkylbenzothieno[2,3-c]pyridines. The presence of a pyrylium ring on one of the positions of the phenyl group leads to a mixture of N-amino derivatives and 5H-[2,3]benzothieno[2,3-e]diazepines. In contrast, 1,3-diphenylbenzothieno[2,3-c]pyrylium perchlorate gives exclusively 5H-[2,3]benzothieno[2,3-e]diazepine.L. M. Litvinenko Institute of Physical Organic Chemistry and Coal Tar Chemistry, National Academy of Sciences of Ukraine, Donetsk 340114. Translate from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp 1137–1140, August, 1998.     

Tetracyclic 1,6-methano-[10]annulenes a novel class of steroidal annulenes

Reaction of 19-hydroxyandrosta-4,6-diene-3,17-dione (8b) and the corresponding Δ⁷-compound (8c) with diethyl-(2-chloro-1,1,2-trifluoroethyl)-amine affords 5β,19-cyclo-Δ^1,6- and 5β,19-cyclo-Δ^1,7-3-ketones (4b) and (4c) respectively. Solvolysis experiments with the 19-tosylates of the 19-hydroxy-Δ^4,6- and Δ^4,7-3-ketones (8b) and 8c) are described as alternate approaches to (4b) and (4c). Exposure of 5β,19-cyclo compounds (4b) and (4c) to acetic anhydride-acetic acid-p-toluenesulfonic acid yields the respective 3-acetoxycycloheptatrienes (5a) and (6a). The latter substance (6a) is converted into the novel tetracyclic 1,6-methano-[10]annulene (2a) on exposure to N-bromosuccinimide in boiling carbon tetrachloride. Synthesis of the corresponding 3-methoxy- and 3-desoxy-1,6-methano-[10]annulenes (2b) and (2c) are also described. The NMR spectra of (2a), (2b) and (2c) and related intermediates are discussed.     

Multi-vicinal fluoroalkanes: a new class of organofluorine compounds

"Multi-vicinal fluoroalkanes" are straight-chain alkanes in which each adjacent carbon atom is bonded to one fluorine atom. Such molecules may be regarded as intermediate in structure between alkanes and perfluoroalkanes. The alternate fluoromethylene groups also generate stereogenic centres, which need to be controlled during synthesis. This review will describe our recent progress in the preparation of such single isomer motifs and the study of the conformational behaviour of this new class of organofluorine compounds.     

Imidazo [2, 1-b]-1,3,4-thiadiazoles. A new class of liquid-crystalline compounds

A series of new liquid-crystalline compounds called imidazo [2,1-b]-1,3,4-thiadiazoles has been synthesized. The new compounds contain alkyl, aryl, trans-alkylcyclohexyl groups in positions 2,6 and lateral Br- and CN-substituents in position 5 of the heterocyclic fragment. The new mesogens normally have a wide mesophase range and a high thermal stability (T_c1 ∼ 300° C). The mesophase type depends significantly on the nature and position of the substituents, in particular the cyclohexane ring. Some chemical, physico-chemical and spectral properties of the new compounds have been investigated. The results are compared with the corresponding characteristics of their aromatic and heterocyclic analogues.