Controlling and Predicting Alkyl-Onium Electronic Structure
Frances K. Towers TompkinsLewis G. ParkerRichard M. FogartyJake M. SeymourEkaterina GoussevaDavid C. GrinterRobert G. PalgraveChristopher D. SmithRoger A. BennettRichard P. MatthewsKevin R. J. Lovelock
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Abstract:
X-ray photoelectron spectroscopy (XPS) andKeywords:
Onium
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The liquid-phase oxidation of cyclohexene or tetraline with N2O was studied in various solvents in the presence of onium salts or without them. The onium salts exerted significant promoting effect on the reactions. The activation of the oxidant was studied by IR spectroscopy. It was found that the interactions of the ions in the onium salts and the polarised N–O bond further enhanced polarisation leading to an activation of the oxidant, thus, increasing the rate of oxidation.
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A carbanion, which concomitantly is a part of an onium system, namely an “onium anion” such as (2), could be generated from cations of the dihydrodiazepinium salts, e.g. (1). “Onium anions” can also be postulated as intermediate steps in known reactions.
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Using the method of Van Rossum & Ariëns (1959), a number of bis‐, tris‐ and tetra‐onium neuromuscular blocking agents have been classified into depolarizing, non‐depolarizing and intermediate‐acting compounds. This investigation confirmed the results of experiments using conventional techniques. The role of the ether oxygen link, the effects of inter‐onium distance, alkyl group size and the number and nature of the onium groups were also investigated, and the reasons underlying the observed quantitative and qualitative differences discussed.
Onium
Tetra
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Abstract Quaternary onium salts of halides can be efficiently converted into the corresponding quaternary onium salts of various anions [NO 3 – , BF 4 – , PF 6 – , CF 3 SO 3 – , CH 3 SO 3 – , ClO 4 – , p ‐CH 3 C 6 H 4 SO 3 – , CF 3 CO 2 – , 2,4‐(NO 2 ) 2 C 6 H 3 O – ] by treating the onium halide with trimethyl phosphate under neat condition in the presence of an equivalent amount of conjugate acid of the desired anion.
Onium
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Abstract Linear bis- and tris-onium ethers (I and II) have weak tubocurarine-like properties. In both series, potency increased with increase in alkyl group size. No evidence was found for a one point receptor attachment in bis-onium ethers
Onium
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Studies of analytical systems involving onium and basic
dye cations and solvent extraction methods.
The original intention of this project was to study
selected onium extractions in continuation of previous work
carried out in this laboratory.
The extraction of Cr(VI) with onium salts into organic
solvents had been studied by previous workers who had shown
that Cr(VI) could just as readily be extracted from acid
solution without the addition of an onium salt. A study has
been made of the effect of various onium compounds, and different
organic solvents on this extraction. The effect of pH, as well
as interfering ions was studied. In the present study, in
spite of the colour stability of the complex and the coefficient
of variation being 0.4%, a low apparent molar absorptivity was
obtained. [Continues.]
Onium
Molar absorptivity
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Abstract Preliminary observations upon a series of NNNN-tetra-onium compounds (Ia to Ih), an NNSNN-penta-onium compound (II) and an NNNNNN-hexa-onium compound (III) have so far indicated that inter-onium distance is more important in determining the type of activity than the overall length of the molecule or the number of onium centres it contains.
Onium
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Blocking (statistics)
HEXA
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