direkt zum Inhalt springen

direkt zum Hauptnavigationsmenü

Sie sind hier

TU Berlin

Page Content

Search

Search for publications




all Publications (Reviews, Articles, Meetings and Proceedings)

Anilino radical complexes of cobalt(III) and manganese(IV) and comparison with their phenoxyl analogues
Citation key ISI:000090078900013
Author Penkert, F N and Weyhermuller, T and Bill, E and Hildebrandt, P and Lecomte, S and Wieghardt, K
Pages 9663-9673
Year 2000
ISSN 0002-7863
Address 1155 16TH ST, NW, WASHINGTON, DC 20036 USA
Journal J. Am. Chem. Soc
Volume 122
Number 40
Month OCT 11
Publisher AMER CHEMICAL SOC
Abstract The pendent arm macrocyclic aniline ligands 1-(2-amino-3,5-di-tert-butylbenzyl)-4,7-dimethyl-1,4,7-triazacyclononane , H[L-1], and 1,4,7-tris(2-amino-3,5-di-tert-butylbenzyl)-1,4,7-triazacyclononane, H-3[L-2], have been synthesized. The reaction of these ligands in methanol (1:1) and/or ethanol with Co-II(ClO4)(2). 6H(2)O and potassium di-tert-butylacetylacetonate (1:1) or Mn-II(acetate)(2). 4H(2)O in the presence of air produced the anilide complexes [Co-III(L-1)(Bu(2)acac)](ClO4) (1) and [Mn-IV(L-2)]X (X = ClO4 (2), BPh4 (2')), respectively. The reaction of H-3[L-2] and CuCl2. 2H(2)O in ethanol produced upon addition of NaClO4 blue crystals of [Cu-II(H3L2)Cl](ClO4) (3) containing two coordinated and one uncoordinated aniline pendent arm. Complexes 1, 2, and 3 have been structurally characterized by X-ray crystallography. Electrochemically, 1 is reversibly oxidized with formation of the paramagnetic anilino radical species [Co-III(L-1 .)(Bu(2)acac)(2+) (S = 1/2) whereas the cyclic voltammogram of 2 displays three ligand-centered one-electron-transfer oxidation waves where complexes [Mn-IV(L-2 .)](2+), [Mn-IV(L-2 . .)](3+), and {[Mn-IV(L-2 . . .)](4+) containing one, two, and three coordinated anilino radicals are formed successively. These anilino radical species have been characterized by UV-vis, X-band EPR, and resonance Raman spectroscopy. The characteristic spectroscopic features of coordinated anilino radicals have been elucidated. In the Mn-IV radical species strong intramolecular exchange coupling between the metal ion (t(2)g(3) configuration
Bibtex Type of Publication Article
Download Bibtex entry

Zusatzinformationen / Extras

Quick Access:

Schnellnavigation zur Seite über Nummerneingabe

This site uses Matomo for anonymized webanalysis. Visit Data Privacy for more information and opt-out options.