Studies of phosphazenes. Aminolysis reactions of pentachloro(2′, 2′, 2′-triphenyl-phosphazen-1′-yl) cyclotriphosphazene,N3P3Cl5(NPPh3)

The reactions of pentachloro(2′, 2′, 2′-triphenylphosphazen-1′-yl)cyclotriphosphazene, N₃P₃Cl₅(NPPh₃), with primary and secondary amines have been investigated using diethyl ether, methyl cyanid or benzene as the solvent. The structures of the products obtained, N₃P₃Cl_5minus;nR_n(NPPh₃) [n = 1, R = NHMe, NHBu^t, NMe₂, NC₅H₁₀, NEt₂; n = 2, R = NMe₂, NC₅H₁₀, NEt₂; n = 3, R = NMe₂, NHBu^t; n = 5, R = NMe₂] are elucidated by ¹H and ³¹P NMR spectroscopy. The ? NPPh₃ substituent exerts a pronounced geminal directing influence on incoming secondary amino nucleophiles; compounds containing a ≡ PCl(NPPh₃) group are not formed at the bis and subsequent stages of chlorine replacement. The reactions that involve primary amines follow the pattern established for the analogous reactions of hexachlorocyclotriphosphazene. The effect of solvent and possible mechanism(s) are discussed.     

Novel solid-phase extraction and preconcentration technique coupled with ICP-AES for the determination of Cr(III), Ni(II), and Zn(II) in various water samples

Newly synthesized 2-propylpiperidine-1-carbodithioate (2-PPC) was used for the extraction of Cr(III), Ni(II), and Zn(II) from various water samples. In the present investigation, the use of a syringe loaded with sorbent for the separation and enrichment of Cr(III), Ni(II), and Zn(II) prior to their determination by inductively coupled plasma-atomic emission spectrometry (ICP-AES) was proposed to substitute the batch and column techniques. The described method was compared with the column technique with respect to fastness, simplicity, recovery, and risk of contamination. The syringe was loaded with 1.0 g of sorbent in order to retain the analyte elements. Next, 7.0 mL of sample solution (pH 5.0 ± 0.2) was drawn into the syringe in 15 s and discharged over 15 s. Then, an eluent (3.0 M HCl) was drawn into the syringe and ejected back to desorb the analyte elements. At the optimum conditions, the percentage recoveries of Cr(III), Ni(II), and Zn(II) were in the range of 94.50 to 99.62% with a standard deviation (S.D.) of 0.03%. The elements could be concentrated by drawing and discharging several portions of sample successively and eluting only one time. The detailed study of various interferences proved the method to be highly selective. The risk of contamination is less than that with the column technique. The method was successfully applied to the determination of Cr(III), Ni(II), and Zn(II) in spiked and natural water samples. The results obtained are in good agreement with those obtained by the reported methods at the 95% confidence level. The text was submitted by the authors in English.     

An algebraic approach to q-partial fractions and Sylvester denumerants

The Ramanujan Journal - In 1857, Sylvester established an elegant theory that certain counting functions (which he termed denumerants) are quasi-polynomials by decomposing them into periodic and...     

Local magnetism of Rh in Ni-Rh alloys near the critical composition for ferromagnetism

Local magnetic behaviour of Rh implanted into Ni-Rh alloys near the critical Rh compositionx=0.37 has been studied using the TDPAC method. The observed Curie-Weiss type local susceptibility reflects the presence of large d spin polarization around Rh yielding a total moment of 4.7 _B. Our results show that the magnetism of Rh in the alloys depends strongly on the number of Ni near neighbour atoms.     

Which electron count rules are needed for four-center three-dimensional aromaticity?

A series of charged and neutral four-center n-electron (4c-ne, n = 1-4) molecules based on the adamantane framework, but which include combinations of boron, nitrogen, and phosphorus atoms at bridgehead positions, were studied computationally at the B3LYP/6-31G* level of density functional theory (DFT). The three-dimensional aromaticity, observed earlier for the 1,3,5,7-bisdehydroadamantane dication (1), is found to be general for 4c-2e electron systems. The degree of electron delocalization, evaluated by energetic, geometric, and various magnetic criteria, is quite independent of the molecular symmetry (point groups vary from Td to Cs), the degeneracy of the orbitals, the molecular charges, and the nature of the atoms participating in the delocalized bonding. Although the multiple positive (e.g., in 1 and some of the heteroatom systems) and multiple negative charges are strongly repulsive, the rigid adamantane frameworks help hold the bridgehead atoms within bonding distances with the fewer available electrons. The corresponding 4c-1e doublets are approximately half as aromatic as the 4c-2e singlets based on the same criteria. However, the three-electron systems may either adopt distorted but still four-center delocalized structures, or alternative 3c-2e two-dimensional arrangements in which the fourth bridgehead atom is more distant. There is no need to derive special rules for each point group for 4c-ne systems. Although the three-dimensional stabilization is computed to be quite appreciable, ranging between 10 and 50 kcalmol(-1), this delocalization energy is generally not sufficient to overcome distortion due to strain in higher homologues of 1 and in analogous noncage systems. Among the various 4c-2e homoadamantanedehydro dications studied, only the 1,8-dehydrohomoadamandiyl-3,6-dication forms a three-dimensional aromatic system.     

Temperature-dependent photoelectron spectroscopy of methyl benzoate anions: observation of steric effect in o-methyl benzoate

Temperature-dependent photoelectron spectra of benzoate anion (C6H5CO2(-)) and its three methyl-substituted isomers (o-, m-, p-CH3C6H4CO2(-)) have been obtained using a newly developed low-temperature photoelectron spectroscopy apparatus that features an electrospray source and a cryogenically controlled ion trap. Detachment channels due to removing electrons from the carboxylate group and benzene ring pi electrons were distinctly observed. Well-resolved vibrational structures were obtained in the lower binding energy region due to the OCO bending modes, except for o-CH3C6H4CO2(-), which yielded broad spectra even at the lowest ion trap temperature (18 K). Theoretical calculations revealed a large geometry change in the OCO angles between the anion and neutral ground states, consistent with the broad ground-state bands observed for all species. A strong steric effect was observed between the carboxylate and the methyl group in o-CH3C6H4CO2(-), such that the -CO2(-) group is pushed out of the plane of the benzene ring by approximately 25 degrees and its internal rotational barrier is significantly reduced. The low rotational barrier in o-CH3C6H4CO2(-), which makes it very difficult to be cooled vibrationally, and the strong coupling between the OCO bending and CO2 torsional modes yielded the broad PES spectra for this isomer. It is shown that there is no C-H...O hydrogen bond in o-CH3C6H4CO2(-), and the interaction between the carboxylate and methyl groups in this anion is found to be repulsive in nature.     

Addition of grignard reagents to aryl acid chlorides: an efficient synthesis of aryl ketones

[chemical reaction: see text]. Direct addition of Grignard reagents to acid chlorides in the presence of bis[2-(N,N-dimethylamino)ethyl] ether proceeds selectively to provide aryl ketones in high yields. A possible tridentate interaction between Grignard reagents and bis[2-(N,N-dimethylamino)ethyl] ether moderates the reactivity of Grignard reagents, preventing the newly formed ketones from nucleophilic addition by Grignard reagents.