Ketovinylation of rhenium pentacarbonyl anion

Conclusions The reaction of-chlorovinylketone with anion [Re(CO)₅]^– gives a mixture of cis- and trans-o-complexes RCOCH=CHRe(CO)₅ and cyclic compounds with known coordination of the ketone group.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1576–1578, July, 1971.     

Discharge of nickel ions in presence of zinc ions

Summary The present results confirm conclusively the inference drawn earlier [2] regarding the role of adsorption of zinc ions on the basis of galvanostatic studies on solid substrates which is also the conclusion drawn by Yurev and Volkov [3] by their recent work on solid substrates.

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Zusammenfassung Bei galvanostatischen Untersuchungen an festen Medien über die Bedeutung der Adsorption von Zinkionen konnten die Ergebnisse einer früheren eigenen Arbeit [2] sowie der Arbeit von Yurev u. Volkov [3] bestätigt werden. Aufgrund potentiodynamischer und potentiostatischer Versuche mit der Quecksilber-Tropfelektrode konnte festgestellt werden, daß die Abscheidungsgeschwindigkeit von Nickel aus Nickelbädern durch Zusatz von Zinkionen herabgesetzt wird. Die Vorteile einer Quecksilber-Tropfelektrode für solche Untersuchungen werden aufgezeigt und interessante Besonderheiten im Verhalten der Strom-Zeit-Kurve während des Wachstums des Tropfens diskutiert.

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Dedicated to Prof. Dr. M. von Stackelberg on his 70th birthday.     

Fragmentation of electrospray-produced oligodeoxynucleotide ions adducted to metal ions

In this article, we describe the unique fragmentations of oligodeoxynucleotides (ODNs) whose phosphate groups are completely depleted of protons and replaced with metal ions. The production of the ubiquitous [a(n) - base] ions still occurs, but no longer by transfer of an acidic phosphate proton to an adjoining 3' base. Nor is the extent of the reaction determined by the proton affinity of that base. Rather, the reaction now occurs via a cleavage 3' to both pyrimidines and purines; cleavage 3' to pyrimidine is more favorable than that 3' to purine. We also demonstrate that an ODN is more stable in the gas phase when its phosphate groups are bound to metal ions than when its phosphate groups are attached to hydrogens. This study also provides further evidence for the ODN fragmentation mechanism that involves H transfer to a nucleobase. To establish the structural utility of this new fragmentation, we applied it to distinguishing small ODNs containing a photomodified cis,syn-cyclobutane pyrimidine dimer from the parent ODNs, a system that cannot be distinguished by collisional activation of precursor species that do not contain metal ions.     

Formation of iminium ions by fragmentation of a2 ions

Tandem mass spectrometric experiments have been carried out on the protonated amides H-Gly-Ala-NH2, H-Ala-Gly-NH2, H-Ala-Val-NH2, H-Val-Ala-pNA, H-Leu-Phe-NH2, H-Phe-Leu-NH2, H-Phe-Tyr-NH2 and H-Tyr-Phe-NH2 with particular emphasis on the fragmentation of the isomeric a2 ions derived therefrom. Primary fragmentation reactions of the protonated amides involve formation of the y1" and b2 ions with further fragmentation of the b2 ion to form the a2 ion which fragments to form iminium ions. Collision-induced dissociation studies of the mass-selected a2 ions were carried out. For the Gly-Ala, Ala-Gly and Val-Ala a2 ions, weak signals were observed corresponding to loss of CO from the a2 ion. With the exception of the Gly-Ala, Ala-Gly and Val-Ala a2 ions, both possible iminium ions (a1 and the internal iminium ion) are observed with the most abundant being that formed by proton attachment to the imine of higher proton affinity. The results provide strong support for the recently proposed (El Aribi et al. J. Am. Chem. Soc. 2003; 125: 9229) mechanism of fragmentation of a2 ions which involves elimination of CO from the a2 ion to form a proton-bound complex of two imines. Based on this mechanism ab initio calculations of the total energies of the a2 ions and the transition states for fragmentation have been carried out giving the energy barrier for fragmentation of each a2 ion. The experimental results are interpreted in terms of these energetics data, unimolecular rate constants calculated by using the RRKM theory, and the imine proton affinities.     

Charge reversal of three alkylamide ions: Free nitrenium ions

The methylnitrenium, ethylnitrenium and dimethylnitrenium ions are prepared by charge reversal collisional activation (CR CA) of the corresponding negative ions; their collisional activation mass spectra are shown to support the assigned structures. MINDO/3 energies are used to evaluate relative energies of [CH₄N]⁺ and [C₂H₆N]⁺ isomers, and to determine whether unstable forms rearrange spontaneously to stable ones. As in other examples, charge reversal here generates cations that do not exist in an energy well, but their transient existence is established because their fragmentation is more rapid than their rearrangement to a more stable form.     

p-Ferrocenyltriphenylcarbonium ions

Conclusions The reactions of the tetraphenylborates of some phenylogs of -ferrocenylcarbonium ions with piperidine were studied.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2175–2177, September, 1978.     

Distonoid ions

By Yates, Bouma, and Radom's definition, distonic radical ions are those formally arising by ionization of diradicals or zwitterionic molecules (including ylides). These ions differ, therefore, from conventional radical ions by displaying the charge site and unpaired electron site (spin) localized mandatorily on separate atoms or group of atoms; that is, these sites are separated in all of their major resonance forms. Many conventional radical ions with a major resonance form in which charge and spin sites reside formally on the same atom or group of atoms display, however, high degree of discretionary (non-mandatory) charge-spin separation. By analogy with the metal/metalloid terminology, we propose that these distonic-like radical ions be classified as distonoid ions. Radical ions would, therefore, be divided into three sub-classes: conventional, distonic, and distonoid ions. B3LYP/6-311 + G(d,p) calculations for a proof-of-principle set of radical cations are used to demonstrate the existence of many types of distonoid ions with a high degree of discretionary charge-spin separation. Reliable calculations are indispensable for probing distonoid ions, since an ion that was expected to be distonoid (by the analysis of its resonance forms) is shown by the calculations to display a characteristic conventional-ion electronic distribution. Similarly to many distonic radical ions, and in sharp contrast to a conventional radical ion (ionized 1,4-dioxane), the gas-phase intrinsic bimolecular reactivity with selective neutrals of a representative distonoid ion, ionized 2-methylene 1,3-dioxolane, is found to include dual ion-radical type reactions.     

Covalent modification of gaseous peptide ions with N-hydroxysuccinimide ester reagent ions

Covalent modification of primary amine groups in multiply protonated or deprotonated polypeptides in the gas phase via ion/ion reactions is demonstrated using N-hydroxysuccinimide (NHS) esters as the modifying reagents. During the ion/ion reaction, the peptide analyte ions and the NHS or sulfo-NHS based reagent form a long-lived complex, which is a prerequisite for the covalent modification chemistry to occur. Ion activation of the peptide-reagent complex results in a neutral NHS or sulfo-NHS molecule loss, which is a characteristic signature of covalent modification. As the NHS or sulfo-NHS group leaves, an amide bond is formed between a free, unprotonated, primary amine group of a lysine side chain in the peptide and the carboxyl group in the reagent. Subsequent activation of the NHS or sulfo-NHS loss product ions results in sequence informative fragment ions containing the modification. The N-terminus primary amine group does not make a significant contribution to the modification process; this behavior has also been observed in solution phase reactions. The ability to covalently modify primary amine groups in the gas phase with N-hydroxysuccinimide reagents opens up the possibility of attaching a wide range of chemical groups to gaseous peptides and proteins and also for selectively modifying other analytes containing free primary amine groups.     

Chemistry of thiophenium ions

Data are reviewed for the generation and reaction of 2H-thiophenium ions which are cationic thiophene -complexes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 733–743, June, 1992.     

Stability of molecular ions

Physical Institute, Leningrad State University. Translated from Zhurnal Strukturnoi Khimii, Vol. 32, No. 5, pp. 133–134, September–October, 1991.     

Dynamics of lithium ions in bismuthate glasses: influence of strontium ions

The influence of strontium ions on the relaxation dynamics of lithium ions in bismuthate glasses has been investigated in the frequency range of 10 Hz to 2 MHz. We have observed that the conductivity increases and the activation energy decreases with the increase of SrO content in the glass compositions with fixed Li2O content. We have also observed that the conductivity increases and the activation energy decreases when Sr2+ ions are replaced by Li+ ions, keeping the glass former content fixed. We have shown that the estimated mobile ion concentration is almost independent of temperature and SrO content in the compositions. We have further shown that a fraction of total lithium ions are mobile for all glass compositions. The results have been interpreted on the basis of the modification of the bismuthate network by the addition of SrO, which enhances the mobility of Li ions, without altering the mobile Li+ ion concentration. We have also shown that the conductivity relaxation in these glasses is independent of temperature and composition, and the nonexponential parameter is less than that for the lithium bismuthate glasses without SrO.     

Electrofocusing of inorganic ions

The mechanism of formation of apH gradient along a paper strip is discussed, and an equation has been derived making possible the calculation of thepH along the carrier. An equation is given relating thepH and the place of ion focusing to the stability constant. The distances between the focused zones have been estimated for the system Fe−Sr−Y, and the results are compared with the experimental data.     

Stability of ferrocenylcarbonium ions

Russian Chemical Bulletin -     

Photodissociation of trapped ions

The ion-trapping ion cyclotron resonance spectrometer, or Fourier transform mass spectrometer, provides a powerful and convenient environment for the study of photodissociation of gas-phase ions. This capability has been explored for about 30 years in a number of laboratories including our own. A variety of developments and applications, historical and current, are organized here under five broad headings: (1) optical spectroscopy of ions; (2) kinetics of the dissociation process; (3) dynamics of the dissociation process; (4) thermochemistry of dissociation; and (5) probing the structure and energy of the ions.