Radical anions.  Electron affinities of benzene, naphthalene,and anthracene having formyl, cyano, and nitro substituents

Chowdhury, Swapan K.; Heinis, Thomas; Kebarle, P.

doi:10.1021/ja00275a074

Cited by 15 publications

(17 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Both structures show comparable stability but their optimized geometries are very different. In addition, previous STO-3G calculations performed for a set of singly substituted benzene radical anions (35) reveal that the 'kstate is favoured by T-electron donor substituents while the ' B state is preferred by T-electron acceptor groups. The expansion of T conjugation or the introduction of electron-withdrawing substituents stabilizes the radical anion, extending the T*-type SOMO electron density over the aromatic ring and over the substituent.…”

Section: Molecular Structuresmentioning

confidence: 89%

Abinitio study on radical anions of nitro compounds

Ramondo¹

1992

Can. J. Chem.

View full text Add to dashboard Cite

This paper is dedirnted to Professor Sigeru Huzinaga on the occasion of his 65th birthdayFABIO RAMONDO. Can. J. Chem. 70, 3 14 (1992).The results of ab itritio molecular orbital calculations on some nitro compounds, RN02 (R = CH,, CF,, CH,F, BH,, BF,, BHF, C6H5) and on the corresponding radical anions are reported. The geometries of the neutral and charged species were optimized at the SCF and MP2 levels of theory employing the 6-31G* and the 6-3 1 +G* basis sets. The rotation about the CN and BN bonds reveals distinct conformations for each molecule and vibrational frequencies were determined for such structures. All the employed levels of theory predict structural differences between neutral and charged molecules. The major geometrical changes occurring by electron adding to R N 0 2 consist in the lengthening of the NO bonds and in the shortening of the CN and BN bonds. The radical anions are calculated to be pyramidal at nitrogen in the stable conformers of CH,NO,-, CF3N02-, CH,FNO,-, while, for the T-electron-accepting substituents (BH,, BHF, BF,, C6H5), the anion is planar. Electron correlation energy corrections in the framework of Moiler-Plesset perturbation theory were included to determine relative stabilities between different conformations. At the MP4/6-3 1G*//MP2/ 6-31G* level, an easy rotation of the NO, group is predicted for all the radical anions and neutral molecules with the exception of BH?NO,-, BF2N02-, and BHFN0,-, which show high torsional barriers about the BN bond.

show abstract

Section: Molecular Structuresmentioning

confidence: 89%

Abinitio study on radical anions of nitro compounds

Ramondo¹

1992

Can. J. Chem.

View full text Add to dashboard Cite

show abstract

“…65 Systematic determinations of thermal rate constants kx were undertaken in the reviewers' laboratory from 1984 onward. 37,38,40,[42][43][44][45][46] A description of the method of measurement is given in Grimsrud.37 Some 90 rate constants were determined. Part of these are summarized in Table I.…”

Section: Kinetics Of Electron-transfer Reactionsmentioning

confidence: 99%

“…In these systems charge delocalization in the unsubstituted compound (nitrobenzene") is due to delocalization onto the N02 group. 44 More extensive EA data are available for substituted nitrobenzenes from ETE determinations in both Mclver's and Kebarle's laboratory (see Table II). A plot of the substituent effects is shown in Figure 11.…”

Section: Electron Affinities: Structures and Stabilities Of Radical A...mentioning

confidence: 99%

See 1 more Smart Citation

Electron affinities and electron-transfer reactions

Kebarle¹,

Chowdhury²

1987

Chem. Rev.

Self Cite

297

154

View full text Add to dashboard Cite

“…This multitude of binding geometries was later experimentally and theoretically established from electron affinities measured from gas-phase ion-molecule equilibrium measurements with pulsed electron high ion source pressure mass spectrometers [17][18][19][20][21][22][23] and supporting molecular orbital discussions/calculation. [24][25][26][27][28] Interestingly, gas-phase techniques have resurfaced as a popular method to study related anion-arene interactions. 29,30 2.…”

Section: Introductionmentioning

confidence: 99%

Experimental evidence for interactions between anions and electron-deficient aromatic rings

2009

View full text Add to dashboard Cite

This feature article summarizes our research aimed at using electron-deficient aromatic rings to bind anions in the context of complementary research in this active field. Particular attention is paid to the different types of interactions exhibited between anions and electron-deficient arenes in solution. The 120+ references cited in this article underscore the flurry of recent activity by numerous researchers in this field, which was relatively nascent when our efforts began in 2005. While the interaction of anions with electron-deficient aromatic rings has recently garnered much attention by supramolecular chemists, the observation of these interactions is not a recent discovery. Therefore, we begin with a historical perspective on early examples of anions interacting with electron-deficient arenes. An introduction to recent (and not so recent) computational investigations concerning anions and electron-deficient aromatic rings as well as a brief structural survey of crystalline examples of this interaction are provided. Finally, the limited solution-based observations of anions interacting with electron-deficient aromatic rings are summarized to introduce our current investigations in this area. We highlight three different systems from our lab where anion-arene interactions have been investigated. First, we show that tandem hydrogen bonds and anion-arene interactions augment halide binding in solution. Second, a crystallographic and computational study highlights the multiple types of interactions possible between anions and electron-deficient arenes. Third, we summarize the first example of a class of designed receptors that emphasize the different types of anion-arene interactions possible in solution.

show abstract

Radical anions. Electron affinities of benzene, naphthalene,and anthracene having formyl, cyano, and nitro substituents

Cited by 15 publications

References 0 publications

Abinitio study on radical anions of nitro compounds

Abinitio study on radical anions of nitro compounds

Electron affinities and electron-transfer reactions

Experimental evidence for interactions between anions and electron-deficient aromatic rings

Contact Info

Product

Resources

About