Spectrophotometric determination of traces of gallium and indium with 1-(2-pyridylazo)-2-naphthol

1-(2-Pyridylazo)-2-naphthol (PAN) reacts with either gallium or indium at pH 5–6 giving a red complex in an aqueous medium in the presence of N.N-dimethyl-formamide. The maximum absorption of both PAN complexes of gallium and indium in an aqueous solution is at 545 mμ. The gallium-PAN complex shows a characteristic enhancement of color by addition of small amounts of ethers. Based on this selective enhancement reaction, gallium can be determined in the presence of other metals without separation. The results of determining gallium and indium in the presence of each other are reported. Both gallium and indium form M₂(PAN)₃; but in the presence of certain organic solvents, a different gallium complex, Ga(PAN)₅, and the same indium complex, In₂(PAN)₃, are formed. The reaction of PAN with cadmium can be masked by iodide; an example of determining indium in the presence of cadmium is given. The PAN method has a sensitivity of 0.003 μg/cm² for gallium and 0.005μg/cm² for indium and an absorptivity of 24,900 for the Ga-PAN complex and of 24,500 for the In-PAN complex, respectively. The methods have been successfully applied to the determination of both gallium and indium in germanium thin films.     

Vinyl sulfones in solid-phase synthesis: preparation of 4,5,6,7-tetrahydroisoindole derivatives

The preparation of functionalized 4,5,6,7-tetrahydroisoindole via a traceless solid-phase sulfone linker strategy is described. Thermolytic extrusion of SO(2) from polymer-bound 3-(phenylsulfonyl)-3-sulfolene (7) generated polymer-bound 2-(phenylsulfonyl)-1,3-butadiene (9) in situ which underwent Diels--Alder cycloaddition with various dienophiles to furnish vinyl sulfone resins 10-14. To complete a traceless linker cleavage strategy, (p-tolysulfonyl)methyl isocyanide or ethyl isocyanoacetate was employed to react with the vinyl sulfone moiety to liberate functionalized 4,5,6,7-tetrahydroisoindole products from the resin. Using this chemistry, nine tetrahydroisoindole derivatives (6, 15-22) were prepared in 32-41% overall yields from polystyrene/divinylbenzene sulfinate 1.     

Thiazolium-mediated multicomponent reactions: a facile synthesis of 3-aminofuran derivatives

[reaction: see text] A facile synthesis of highly functionalized 3-aminofuran derivatives by the multicomponent reactions of thiazolium salts, aldehydes, and DMAD is described.     

π -Type and σ -type cation- π complexes of atomic cations

MP2/6-31+G* calculations were performed on the cation- complexes of ethylene, cyclobutadiene and benzene with a number of atomic cations. It was found that except B⁺ all the atomic cations form -type cation- complexes with ethylene. On the other hand, with cyclobutadiene Li⁺, N⁺, Na⁺, P⁺ and K⁺ form -type complexes, whereas H⁺, F⁺, and Cl⁺ form covalent -type complexes. With benzene Li⁺, B⁺, Na⁺, Al⁺, and K⁺ form -type complexes whereas H⁺, F⁺, and Cl⁺ form -type complexes. It was concluded that the driving force to form the -type complex is chemical bonding, and that for metal cations to form -type complexes is non-covalent interaction.     

The photophysics of monomeric bacteriochlorophylls c and d and their derivatives: properties of the triplet state and singlet oxygen photogeneration and quenching

Measurements of pigment triplet-triplet absorption, pigment phosphorescence and photosensitized singlet oxygen luminescence were carried out on solutions containing monomeric bacteriochlorophylls (Bchl) c and d, isolated from green photosynthetic bacteria, and their magnesium-free and farnesyl-free analogs. The energies of the pigment triplet states fell in the range 1.29-1.34 eV. The triplet lifetimes in aerobic solutions were 200-250 ns; they increased to 280 +/- 70 microseconds after nitrogen purging in liquid solutions and to 0.7-2.1 ms in a solid matrix at ambient or liquid nitrogen temperatures. Rate constants for quenching of the pigment triplet state by oxygen were (2.0-2.5) x 10(9) M-1 s-1, which is close to 1/9 of the rate constant for diffusion-controlled reactions. This quenching was accompanied by singlet oxygen formation. The quantum yields for the triplet state formation and singlet oxygen production were 55-75% in air-saturated solutions. Singlet oxygen quenching by ground-state pigment molecules was observed. Quenching was the most efficient for magnesium-containing pigments, kq = (0.31-1.2) x 10(9) M-1 s-1. It is caused mainly by a physical process of singlet oxygen (1O2) deactivation. Thus, Bchl c and d and their derivatives, as well as chlorophyll and Bchl a, combine a high efficiency of singlet oxygen production with the ability to protect photochemical and photobiological systems against damage by singlet oxygen.     

SiH+5 and the proton affinity of monosilane

Tandem mass spectrometric studies show that SiH⁺₅ is formed in bimolecular reactions of SiH₄ and NH⁺₂, C₂H⁺₃, C₂H⁺₆ and C₃H⁺₈ ions. The dependence of the reaction cross sections on ion energy indicates the formation of SiH⁺₅ from NH⁺₂, C₂H⁺₃, and C₂H⁺₆ to be exothermic reactions, while formation from C₃H⁺₈ is endothermic. Using known thermochemical data, these facts permit the assignment of 150 and 156 kcal/mole to the lower and upper limits of the proton affinity of monosilane.     

Theoretical Study of Weakly Bound Dimers between Hydrogen Fluoride and Some Polar Molecules

Weakly bound linear and bent dimers, FH—X (where X = CO, OC, CNH, NCH, N₂O and ON₂), are investigated using the DFT B3LYP and ab initio MP2 methods with the same basis sets (6–311++G(3df,2pd)). The strengths of the H—C or H—N H‐bonds in dimers FH—CO, FH—CNH, and FH—N₂O are compared with those of the H—O or H—N H‐bonds in dimers FH—OC, FH—NCH, and FH—ON₂. The results obtained for the H‐bond distances, the elongation effect of the HF bond, the red shift of the HF stretching frequency, and the energy difference between the dimer and the charge transfer reveal that the H‐bonds of the first group of dimers are stronger than those of the second. The Gibbs energies calculated for the six dimer formations indicate that the weakly bound dimers are unstable at room temperature (T = 298 K) (FH—X's → FH + X's, ΔG < 0).     

Remote substituent effects on bond dissociation energies of para-substituted aromatic silanes

UB3LYP/6-31G(d) and ROMP2/6-311++G(d,2p) methods were used to calculate the Si-X bond dissociation energies (BDEs) of a number of para-substituted aromatic silanes (4-Y-C(6)H(4)-SiH(2)X, where X = H, F, Cl, or Li). It was found that the substituent effect on the Si-H BDE of 4-Y-C(6)H(4)-SiH(3) was small, as the slope (rho(+)()) of the BDE- regression was only 0.09 kJ/mol. In comparison, the substituent effect on the Si-F BDE of 4-Y-C(6)H(4)-SiH(2)F was much stronger, whose rho(+ )()value was -2.34 kJ/mol. The substituent effect on the Si-Cl BDE of 4-Y-C(6)H(4)-SiH(2)Cl was also found to be strong with a rho(+)() value of -1.70 kJ/mol. However, the substituent effect on the Si-Li BDE of 4-Y-C(6)H(4)-SiH(2)Li was found to have a large and positive slope (+9.12 kJ/mol) against. The origin of the above remarkably different substituent effects on the Si-X BDEs was found to be associated with the ability of the substituent to stabilize or destabilize the starting material (4-Y-C(6)H(4)-SiH(2)X) as well as the product (4-Y-C(6)H(4)-SiH(2)* radical) of the homolysis. Therefore, the direction and magnitude of the effects of Y-substituents on the Z-X BDEs in compounds such as 4-YC(6)H(4)Z-X should have some important dependence on the polarity of the Z-X bond undergoing homolysis. This conclusion was in agreement with that from earlier studies (for example, J. Am. Chem. Soc. 1991, 113, 9363). However, it indicated that the proposal from a recent work (J. Am. Chem. Soc. 2001, 123, 5518) was unfortunately not justified.     

Photochemical Reaction of Decacarbonyldirhenium with Thiophene and Crystal Structure of Tetradecacarbonylhydridotrirhenium

The photochemical reaction of Re₂(CO)₁₀ with thiophene in hexane solution was investigated under vacuum. Three rhenium clusters: H₂Re₃(CO)₁₂, HRe₃(CO)₁₄ and Re₃(CO)₁₄(OH)₄, were isolated. The structure of Fellmann-Kaesz cluster Complex HRe₃(CO)₁₄ was determined by use of the X-ray diffraction method. The three rhenium atoms form a plane of symmetry and L: Re₁Re₂Re₃ is 107°. The ten carbonyl groups bonded to the two terminal rhenium atoms Re₁ and Re₃, are staggered with respect to the central rhenium atoms. The bond lengths are 3.10 Å for Re₂-Re₃ and 3.34 Å for Re₁-Re₂. The bridging hydride is between Re₁ and Re₂.