Tetracyanoethylene Anion Radical Research Articles

Thermal effect on the electron donating and accepting properties of Na-Y zeolite, and the reduction of SO 2 and CO

A study was made of the formation of phenothiazine cation radical (TPQD +) and tetracyanoethylene anion radical (TCNE −) on the surface of Na-Y zeolite. It was observed using electron spin resonance (e.s.r.) that the number of cation formation sites decreased with higher activation temperature while the number of anion sites increased, the respective changes not being in proportion. The formation of the SO 2 − anion radical on Na-Y zeolite was studied at 450°C. It was observed that the e.s.r. line intensity of SO 2 − increased with the reaction time, and also with the length of degassing time during thermal activation. CO + cation radicals were formed when the SO 2-treated zeolite was heated at 450°C in contact with CO. The CO + radicals disappeared either on prolonged heating or heating in the presence of air. The SO 2 ions do not take part in the reduction of SO 2 − with the CO over zeolite. Mechanisms for the formation of CO + and the other observed effects is discussed.

A Rotating Disk Cell for Raman Spectroelectrochemistry: Investigation of an Electrode Surface Species and an Electrogenerated Solution Species

A Raman spectroelectrochemical cell has been developed which incorporates a rotating disk design. This cell has been shown to be useful for the Raman investigation of electrode surface species (spinning electrode) and electrogenerated solution species (static electrode). It has been used to characterize the Raman spectroelectrochemical behavior of photolabile dithizone anion adsorbed at silver and copper electrode surfaces. Use of this cell for the study of electrogenerated solution species was demonstrated by the resonance Raman characterization of the tetracyanoethylene anion radical electrogenerated with a cyclic potential step. Cell construction is described and its merits discussed.

ESR investigation of tetracyanoethylene anion radical with magnesium as counterion

The tetracyanoethylene anion radical formed by the reaction of metallic magnesium of anhydrous magnesium halides with TCNE in tetrahydrofuran shows an esr spectrum whose features differ from the spectrum of TCNE − obtained by other methods; the hyperfine splitting pattern indicates a weak interaction of TCNE radical with the metal through a nitrogen end of the molecule.

ChemInform Abstract: ELECTRON SPIN RESONANCE STUDIES OF ION PAIR COMPLEXES INVOLVING THE TETRACYANOETHYLENE ANION RADICAL

Chemischer InformationsdienstVolume 7, Issue 14 Physical Organic Chemistry ChemInform Abstract: ELECTRON SPIN RESONANCE STUDIES OF ION PAIR COMPLEXES INVOLVING THE TETRACYANOETHYLENE ANION RADICAL M. P. EASTMAN, M. P. EASTMANSearch for more papers by this authorD. A. RAMIREZ, D. A. RAMIREZSearch for more papers by this authorC. D. JAEGER, C. D. JAEGERSearch for more papers by this authorM. T. WATTS, M. T. WATTSSearch for more papers by this author M. P. EASTMAN, M. P. EASTMANSearch for more papers by this authorD. A. RAMIREZ, D. A. RAMIREZSearch for more papers by this authorC. D. JAEGER, C. D. JAEGERSearch for more papers by this authorM. T. WATTS, M. T. WATTSSearch for more papers by this author First published: April 6, 1976 https://doi.org/10.1002/chin.197614042AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume7, Issue14April 6, 1976 RelatedInformation

ChemInform Abstract: EFFECT OF CESIUM COUNTERION ON THE ESR SPECTRUM OF TETRACYANOETHYLENE ANION RADICALS

Chemischer InformationsdienstVolume 5, Issue 39 Physical Organic Chemistry ChemInform Abstract: EFFECT OF CESIUM COUNTERION ON THE ESR SPECTRUM OF TETRACYANOETHYLENE ANION RADICALS MASAAKI OGASAWARA, MASAAKI OGASAWARASearch for more papers by this authorSEIZO INABA, SEIZO INABASearch for more papers by this authorHIROSHI YOSHIDA, HIROSHI YOSHIDASearch for more papers by this authorKOICHIRO HAYASHI, KOICHIRO HAYASHISearch for more papers by this author MASAAKI OGASAWARA, MASAAKI OGASAWARASearch for more papers by this authorSEIZO INABA, SEIZO INABASearch for more papers by this authorHIROSHI YOSHIDA, HIROSHI YOSHIDASearch for more papers by this authorKOICHIRO HAYASHI, KOICHIRO HAYASHISearch for more papers by this author First published: October 1, 1974 https://doi.org/10.1002/chin.197439090AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume5, Issue39October 1, 1974 RelatedInformation

Effect of Cesium Counterion on the ESR Spectrum of Tetracyanoethylene Anion Radicals

Abstract Evidence was obtained by ESR for the ion-pair formation between the tetracyanoethylene anion radical and the cesium counterion in tetrahydrofuran. The hyperfine lines of the ESR spectrum of cesium tetracyanoethylenide were exceptionally broad at high salt concentrations in tetrahydrofuran, while they were remarkably narrowed by the addition of a small amount of DMF or triglyme (cation-solvating agents) or by replacing the counterion with the tetra-n-butylammonium ion. This indicates that the broad linewidth is due to the unresolved hyperfine splitting of the cesium counterion. In addition, the concentration dependence of the ESR spectrum indicates that the line broadening is to be interpreted not only in terms of the Heisenberg spin exchange, but also in terms of the equilibrium between the ion-pair and the free ion. The cesium hyperfine coupling constant was estimated by simulating the line shape to be 40 m Gauss in the ion-pair state between the tetracyanoethylene anion radical and the cesium ion in the tetrahydrofuran solution.

Radical-ion formation in aromatic amine–tetracyanoethylene systems

The kinetics of the formation and decay of the tetracyanoethylene radical anion from aromatic amine–tetracyanoethylene systems in dichloromethane have been studied. A mechanistic scheme to account for the observed reaction products and kinetic order is proposed and reaction with an excess of donor is suggested to be the major pathway within this mechanism.

Electron spin resonance studies of the effect of ion pairing on some simple reactions involving the tetracyanoethylene anion radical

Electron spin resonance studies of the effect of ion pairing on some simple reactions involving the tetracyanoethylene anion radical

ChemInform Abstract: VIBRONIC INTERACTIONS, RESONANCE RAMAN SPECTRA AND BOND STRENGTHS FOR THE RADICAL ANION SALTS OF TETRACYANOETHYLENE

Raman spectra for the intensely colored salts of the tetracyanoethylene radical anion with sodium and potassium cations confirm previous assertions that the infrared salt spectra are completely dominated by vibronic interaction effects. As expected, strong Raman scattering has been observed at frequencies coincident with the intense infrared bands which have been assigned to totally symmetric modes activated by an ``electron‐vibration'' moment. The scattering intensities of the symmetric stretching modes (ν1, ν2, and ν3) reveal a complex dependence on excitation frequency which is qualitatively consistent with the observed vibronic structure of the electronic absorption band. By confirming the assignment of several of the radical anion internal modes, the Raman data have also permitted the evaluation of reliable stretching constants for comparison with the neutral molecule force constants and quantum chemical predictions of bond order changes. New data and a subsequent force constant analysis have required the reassignment of

Vibronic interactions, resonance Raman spectra and bond strengths for the radical anion salts of tetracyanoethylene

Raman spectra for the intensely colored salts of the tetracyanoethylene radical anion with sodium and potassium cations confirm previous assertions that the infrared salt spectra are completely dominated by vibronic interaction effects. As expected, strong Raman scattering has been observed at frequencies coincident with the intense infrared bands which have been assigned to totally symmetric modes activated by an ``electron-vibration'' moment. The scattering intensities of the symmetric stretching modes (ν1, ν2, and ν3) reveal a complex dependence on excitation frequency which is qualitatively consistent with the observed vibronic structure of the electronic absorption band. By confirming the assignment of several of the radical anion internal modes, the Raman data have also permitted the evaluation of reliable stretching constants for comparison with the neutral molecule force constants and quantum chemical predictions of bond order changes. New data and a subsequent force constant analysis have required the reassignment of

The Electronic States of Tetracyanoethylene and Its Anion Radical as Studied by Their Infrared Spectra

Abstract The infrared spectra of tetracyanoethylene (TCNE) and its anion radical in the rock-salt region were examined in order to observe any appreciable frequency differences between their corresponding bands. The vibrational assignments were made, and the basic Urey-Bradley force field was determined for the TCNE anion radical. By comparing them with those of the neutral TCNE, we discussed the difference in the electronic states between the neutral TCNE and its anion radical. The half-occupied molecular orbital of the TCNE anion radical was found to belong to the B2g irreducible representation.

Counterion Effect in the Electron-Transfer Reactions between a Tetracyanoethylene Radical Anion and Its Neutral Molecule

Abstract The rates of homogeneous electron-transfer reactions between radical anions and neutral molecules were studied in a variety of tetracyanoethylenide systems in order to obtain information concerning the counterion effect on the electron-transfer reactions. The estimated values of the rate constants had the same order of magnitude at room temperature for all the systems, while the activation energies and the preexponential factors were markedly dependent on the natures of the counterions and the solvents. The obtained results are discussed in terms of the forms and structures of the radical anions.

Electron density in functional groups of free radicals determined by infrared spectroscopy

Stretching frequencies in the i.r. spectra of several diarylketyl and tetracyanoethylene anion radicals have been compared with the frequencies of the unreduced molecules. Some correlation of known electron densities (from e.s.r. results) and observed stretching frequencies has been attempted. Correlation equations developed apply best for ketyls and tetracyanoethylene.

Charge-transfer complexes: the interactions between tetracyanoethylene and aromatic amines

Charge-transfer complexes between tetracyanoethylene (TCNE) and a number of aromatic amines have been studied in dichloromethane solution. Correlations between transition energies and base strength of the amine or Hammett σ-function for substituents have been noted. Spectroscopic evidence as to the intermediacy of a σ-complex in the reaction between N-methylaniline and TCNE is cited and the presence of the tetracyanoethylene radical anion in the system reported.

Communications- Preparation and Chemistry of Tetracyanoethylene Anion Radical

ADVERTISEMENT RETURN TO ISSUEPREVArticleCommunications- Preparation and Chemistry of Tetracyanoethylene Anion RadicalO Webster, W Mahler, and R BEnsonCite this: J. Org. Chem. 1960, 25, 8, 1470Publication Date (Print):August 1, 1960Publication History Published online1 May 2002Published inissue 1 August 1960https://doi.org/10.1021/jo01078a037RIGHTS & PERMISSIONSArticle Views365Altmetric-Citations47LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (114 KB) Get e-Alerts Get e-Alerts