Density functional study of lithium-aromatic sandwich compounds and their crystals

Using density functional theory, we have theoretically studied the formation of neutral lithium-aromatic complexes R-nLi and R-nLi-R, where R is benzene, naphthalene, or pyrene. We first find that the maximum number of lithium atoms n in the complexes increases with the size of R. In addition, pyrene favors the sandwich compound R-4Li-R over R-4Li more than three times that of the corresponding tendency for benzene, strongly suggesting the possible existence of oligomer (R-4Li)x. We have also investigated energetics and band structures of infinite one-dimensional crystals of R-nLi, finding them metallic. Detailed analysis of the electronic structure shows that all these observations are related to the strong electrostatic interaction among the species, which is originated from the charge transfer from Li atoms to the aromatic rings. In addition, it is shown that the pyrene crystal is mechanically stable with respect to deformation. This also suggests the possibility of its existence, which, in turn, holds potential application in lithium storage in respect to its large Li/C ratio.     

Photoreactions of benzosilacyclobutenes with carbonyl compounds. SH2 reaction on SiC bond by triplet carbonyl compounds

Photoreaction of 2,3-benzo-1,1-diphenyl(or dimethyl)-1-sila-2-cyclobutene with an aldehyde or ketone results in 1:1 cycloadduct of [4+2] type, the formation of which is accountd for in terms of S_H2 process, i.e., attack of a triplet carbonyl compound on the silicon of the benzosilacyclobutene.     

XPS analysis of the effect of Pt addition to Pd catalysts for complete benzene oxidation

Pt-Pd bimetallic catalysts were prepared in order to develop and investigate catalysts having excellent activity and stability for benzene destruction. The effect of Pt addition to Pd catalysts is studied by XPS analysis. This revised version was published online in August 2006 with corrections to the Cover Date.     

Immobilized cobalt/rhodium heterobimetallic nanoparticle-catalyzed silylcarbocylization and carbonylative silylcarbocyclization of 1,6-enynes

Reaction of 1,6-enynes with a hydrosilane in the presence of immobilized cobalt/rhodium bimetallic nanoparticles gives 2-methyl-1-silylmethylidene-2-cyclopentanes in the absence of carbon monoxide and 2-formylmethyl-1-silylmethylidene-2-cyclopentanes under 1 atm of carbon monoxide, respectively. [reaction: see text]     

Facile generation of platinum(IV) compounds with mixed labile moieties. Hydrogen peroxide oxidation of platinum(II) to platinum(IV) compounds

Hydrogen peroxide oxidation of platinum(II) compounds containing labile groups such as Cl, OH, and alkene moieties has been carried out and the products characterized. The reactions of [Pt^II (X)₂ (N–N)] (X = Cl, OH, X₂ = isopropylidenemalorate (ipm); N–N 2,2-dimethyl-1,3-propanediamine [(dmpda), N-isopropyl-1,3-propanediamine (ippda)] with hydrogen peroxide in an appropriate solvent at room temperature affords [Pt^IV (OH)(Y)(X)₂(N–N)] (Y = OH, OCH₃). The crystal structures of [Pt^IV(OH)(OCH₃)(Cl)₂(dmpda)]·2H₂O (P-1 bar, a = 6.339(2) Å , b = 9.861(1) Å, c = 11.561(1) Å, a = 92.078(9)°, β = 104.78(1)°, γ=100.54(1)°, V = 684.3(2) ų, Z = 2R = 0.0503) and [Pt^IV(OH)₂(ipm)(ippda)]·3H₂O (C 2/c, a = 27.275(6) Å, b=6.954(2) Å, c = 22.331(4) Å, β = 118.30(2)°, V = 3729(2) ų, Z = 8, R = 0.0345) have been solved and refined. The local geometry around the platinum(IV) atom approximates to a typical octahedral arrangement with two added groups (OH and OCH₃; OH and OH) in a transposition. The platinum(IV) compounds with potential labile moieties may be important intermediate species for further reactions.     

Sequential actions of cobalt nanoparticles and palladium(II) catalysts: three-step one-pot synthesis of fenestranes from an enyne and an alkyne diester

A three-step one-pot synthesis of fenestranes from a readily available enyne and an alkyne diester has been carried out with cobalt nanoparticles and palladium(II) as catalysts.     

Fluoride-facilitated deuterium exchange from DMSO-d6 to polyamide-based cryptands

Multiple deuterium exchange between DMSO-d6 and amide hydrogens in two hexaamido cryptand fluoride receptors has been verified by 19F and 2H NMR and FAB mass spectral studies. Structural results for one of the complexes indicate a tricapped trigonal prism hydrogen bond coordination geometry around an encapsulated fluoride, with hydrogen bonds from fluoride to six amide and three phenyl hydrogens.     

Co2(CO)8 Catalyzed reaction of oxetanes with trialkylsilanes

Dicobalt octacarbonyl catalyzed silyl-hydroformylation of oxetanes can be controlled by the choice of trialkylsilane. Triethylsilane gives 1,4-$\text{bis}$-silyl ethers while $\text{t}$-butyl-dimethylsilane yields silyl enol ethers.     

Anionic templating: synthesis,structure, and characterization of novel three-dimensional mixed-metal oxychlorides Te(4)M(3)O(15).Cl (M = Nb(5+) or Ta(5+))

Two new three-dimensional oxychlorides are reported, Te(4)M(3)O(15).Cl (M = Nb(5+) or Ta(5+)). The isostructural materials were synthesized by chemical transport reactions utilizing TeO(2), M(2)O(5), and MCl(5) (M = Nb(5+) or Ta(5+)) as reagents. The compounds exhibit a three-dimensional cationic tunnel framework, with Cl(-) anions occupying the tunnels. Crystal data: monoclinic, space group C2/c, a = 18.9944(7) A, b = 7.8314(3) A, c = 21.1658(8) A, beta = 116.6400(10) degrees, Z = 8 (T = 295 K).     

Synthesis of Novel Benzo-15-Crown-5-Tethered β-Cyclodextrins and Their Enhanced Molecular Binding Abilities by Alkali Metal Cation Coordination

Two novel benzo-15-crown-5 tethered β-cyclodextrins 1 and 2have been synthesized by coupling substituted benzo-15-crown-5 with correspondingβ-cyclodextrin derivatives. Their inclusion complexation behavior withrepresentative guests, such as cyclohexanol, cyclohexane carboxylic acid, cyclohexaneacetic acid, sodium cyclohexane carboxylate, and potassium cyclohexane carboxylate,was investigated in aqueous solution by means of fluorescence spectrometry. As compared with parent β-cyclodextrin, benzo-15-crown-5 tethered β-cyclodextrins 1–2 display significantly enhanced molecular binding abilities and selectivities towards model substrates, especially towards substrates containing alkali-metal cations. These results indicate that, bearing two recognition sites in a single molecule, these supramolecular architectures can strongly enhance the molecular binding ability of parent β-cyclodextrin by the cooperative binding of the β-cyclodextrin cavity and the crown ether moiety. Possessing a shorter linker, crown ether-β-cyclodextrin 2 shows much higher binding affinity with guest molecules than crown ether-β-cyclodextrin 1, which may be attributed to the binding size and molecular multiple recognition behavior between host and guest.