scholarly journals EPR and pulsed ENDOR study of intermediates from reactions of aromatic azides with group 13 metal trichlorides

2010 ◽  
Vol 6 ◽  
pp. 713-725 ◽  
Author(s):  
Giorgio Bencivenni ◽  
Riccardo Cesari ◽  
Daniele Nanni ◽  
Hassane El Mkami ◽  
John C Walton
Keyword(s):  
Radical Cations ◽  
Epr Spectra ◽  
Reactive Group ◽  
Group 13 ◽  
Dft Computations ◽  
Unpaired Electrons

The reactions of group 13 metal trichlorides with aromatic azides were examined by CW EPR and pulsed ENDOR spectroscopies. Complex EPR spectra were obtained from reactions of aluminium, gallium and indium trichlorides with phenyl azides containing a variety of substituents. Analysis of the spectra showed that 4-methoxy-, 3-methoxy- and 2-methoxyphenyl azides all gave ‘dimer’ radical cations [ArNHC6H4NH2]+• and trimers [ArNHC6H4NHC6H4NH2]+• followed by polymers. 4-Azidobenzonitrile, with its electron-withdrawing substituent, did not react. In general the aromatic azides appeared to react most rapidly with AlCl3 but this reagent tended to generate much polymer. InCl3 was the least reactive group 13 halide. DFT computations of the radical cations provided corroborating evidence and suggested that the unpaired electrons were accommodated in extensive π-delocalised orbitals. A mechanism to account for the reductive conversion of aromatic azides to the corresponding anilines and thence to the dimers and trimers is proposed.

EPR spectra and structure of the radical cations of fluorinated benzenes

1997 ◽  
pp. 1625-1632 ◽  
Author(s):  
Akinori Hasegawa ◽  
Yoshiteru Itagaki ◽  
Masaru Shiotani
Keyword(s):  
Radical Cations ◽  
Epr Spectra

Guilty and charged: a stable solution of the hexamethylbenzene radical cation as a ligand forming oxidising agent

2018 ◽  
Vol 54 (72) ◽  
pp. 10036-10039 ◽  
Author(s):  
Marcel Schorpp ◽  
Stephan Rein ◽  
Stefan Weber ◽  
Harald Scherer ◽  
Ingo Krossing
Keyword(s):  
Radical Cation ◽  
Stable Solution ◽  
Radical Cations ◽  
Group 13 ◽  
Complex Salts

Arene radical cations as oxidising agents with intended non-innocent behaviour for the synthesis of subvalent Group 13 complex salts.

EPR Spectra and Structure of the Radical Cations of Fluorinated Ethylenes and Propenes

1998 ◽  
Vol 71 (11) ◽  
pp. 2547-2554 ◽  
Author(s):  
Yoshiteru Itagaki ◽  
Masaru Shiotani ◽  
Akinori Hasegawa ◽  
Hisao Kawazoe
Keyword(s):  
Radical Cations ◽  
Epr Spectra

Metallkomplexe mit paramagnetischen Salicylaldimin- und Thiosemicarbazon-Liganden / Metal Complexes of Paramagnetic Salicylaldimine and Thiosemicarbazone Ligands

1971 ◽  
Vol 26 (12) ◽  
pp. 1210-1215 ◽  
Author(s):  
Dieter Jahr ◽  
Karl E. Schwarzhans ◽  
Dietrich Nöthe ◽  
Paul K. Burkert
Keyword(s):  
Free Radicals ◽  
Metal Complexes ◽  
Metal Ion ◽  
Magnetic Moments ◽  
Epr Spectra ◽  
Temperature Dependent ◽  
Unpaired Electrons ◽  
Stable Free Radicals ◽  
Dependent Interaction

A series of complexes formed between metals and the stable free radicals 2,2,6,6-tetramethylpiperidine-1-oxyl-4- (N-salicylaldimine) and 2,2,6,6-tetramethylpiperidone (4) -1-oxyl-thiosemicarba-zone has been prepared. The magnetic moments and the epr spectra of the complexes have been investigated. Some of the complexes show a temperature dependent interaction between the radicalic nitroxyl groups of the ligands. No interaction was found, however, between the metal ion and the unpaired electrons of the ligands.

ChemInform Abstract: EPR Spectra of the Radical Cations of Some Benzocyclobutenes, Benzocyclopentenes and Benzocyclohexenes.

ChemInform ◽  
2010 ◽  
Vol 24 (22) ◽  
pp. no-no
Author(s):  
D. V. AVILA ◽  
A. G. DAVIES ◽  
E. R. LI ◽  
K. M. NG
Keyword(s):  
Radical Cations ◽  
Epr Spectra

EPR spectra for a range of pyrimidine and s-triazine radical cations

1992 ◽  
pp. 1403 ◽  
Author(s):  
Aidan O'Connell ◽  
Ian D. Podmore ◽  
Martyn C. R. Symons ◽  
Jane L. Wyatt ◽  
Franz A. Neugebauer
Keyword(s):  
Radical Cations ◽  
Epr Spectra

Komplexe des Cu(I), Ag(I) und Rh(III) mit Nitronylnitroxylradikalliganden/Complexes of Cu(I), Ag(I) and Rh(III) with Nitronylnitroxylradicals as Ligands

1983 ◽  
Vol 38 (2) ◽  
pp. 265-268 ◽  
Author(s):  
Astrid Dorfer ◽  
Karl E. Schwarzhans
Keyword(s):  
Free Radicals ◽  
Free Radical ◽  
Metal Ions ◽  
Intramolecular Interaction ◽  
Magnetic Moments ◽  
Epr Spectra ◽  
Temperature Dependent ◽  
Stable Free Radical ◽  
Unpaired Electrons ◽  
Meta Isomer

Abstract The stable free radical 4,4,5,5-tetramethyl-imidazoline-1-oxyl-2-p-pyridyl-3-oxide (L1) has been prepared and used as a ligand in copper (I), silver(I) and rhodium(III) complexes, the meta isomer (L2) as a ligand in a rhodium(III) complex, too. The magnetic moments and the EPR spectra of the free radicals and the complexes have been investigated. A solvent and temperature dependent intramolecular interaction between the radicalic ligands was found in the silver(I) complex, but in none of the complexes any intramolecular interaction between the metal ions and the unpaired electrons of the ligands could be observed.

ChemInform Abstract: EPR Spectra for a Range of Pyrimidine and s-Triazine Radical Cations

ChemInform ◽  
2010 ◽  
Vol 23 (49) ◽  
pp. no-no
Author(s):  
A. O'CONNELL ◽  
I. D. PODMORE ◽  
M. C. R. SYMONS ◽  
J. L. WYATT ◽  
F. A. NEUGEBAUER
Keyword(s):  
Radical Cations ◽  
Epr Spectra
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