Evidence for a π dimer in the electrochemical reduction of 1,3,5-trinitrobenzene:: A reversible N2-fixation system

被引：34

作者：

Gallardo, Iluminada ^{[1
]}

Guirado, Gonzalo ^{[1
]}

Marquet, Jordi ^{[1
]}

Vila, Neus ^{[1
]}

机构：

[1] Univ Autonoma Barcelona, Dept Quim, Bellaterra 08193, Barcelona, Spain

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2007年 / 46卷 / 08期

关键词：

azo compounds; electrochemistry; nitrogen fixation; radicals; stacking interactions;

D O I：

10.1002/anie.200602690

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

(Figure Presented) Electrochemical reduction of 1,3,5-trinitrobenzene (1) forms π dimer 2, which evolves to a more stable ω complex. The crystal structure of the NEt4+ salt of 2 shows π-stacked chains of radical anions. Solid 2 or dimeric 2 in solution reacts with N2 to give a dianion in which an azo group links two 1,3,5-trinitrobenzene units (see picture). The azo derivative is reversibly electrochemically oxidized to 1. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：1321 / 1325

页数：5

共 67 条

[1] Synthesis and characterization of a new fluorescent Zwitterionic spirocyclic meisenheimer complex of 1,3,5-trinitrobenzene [J].

Al-Kaysi, RO ;

Guirado, G ;

Valente, EJ .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2004, 2004 (16) :3408-3411

[2] ARE ANION RADICALS UNABLE TO UNDERGO RADICAL RADICAL DIMERIZATION [J].

AMATORE, C ;

PINSON, J ;

SAVEANT, JM .

JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1982, 137 (01) :143-148

[3] MECHANISTIC STUDY OF THE ELECTROCHEMICAL OXIDATION OF SOME AROMATIC-AMINES IN THE PRESENCE OF BASES [J].

ANDRIEUX, CP ;

GALLARDO, I ;

JUNCA, M .

JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1993, 354 (1-2) :231-241

[4] MECHANISTIC STUDIES ON THE ELECTROCHEMICAL REDUCTIVE COUPLING OF SOME POLYHALOGENONITROBENZENES - A NEW EXAMPLE OF A RADICAL-ANION DIMERIZATION [J].

ANDRIEUX, CP ;

BATLLE, A ;

ESPIN, M ;

GALLARDO, I ;

JIANG, ZQ ;

MARQUET, J .

TETRAHEDRON, 1994, 50 (23) :6913-6920

[5] TERMINOLOGY AND NOTATIONS FOR MULTISTEP ELECTROCHEMICAL REACTION-MECHANISMS (IUPAC RECOMMENDATIONS 1994) [J].

ANDRIEUX, CP .

PURE AND APPLIED CHEMISTRY, 1994, 66 (12) :2445-2450

[6]

ANDRIEUX CP, 1986, TECHNIQUES CHEM, V6

[7]

[Anonymous], 1994, ELECT PARAMAGNETIC R

[8] SOME ASPECTS OF ANIONIC SIGMA-COMPLEXES [J].

ARTAMKINA, GA ;

EGOROV, MP ;

BELETSKAYA, IP .

CHEMICAL REVIEWS, 1982, 82 (04) :427-459

[9] ELECTRO-ORGANIC REACTIONS .4. PREPARATIVE ASPECTS OF CATHODIC HYDROGENATION OF ACTIVATED CARBON-CARBON DOUBLE-BONDS [J].

AVACA, LA ;

UTLEY, JHP .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1975, (10) :971-974

[10] MECHANISM OF REACTION OF HYDROXIDE ION WITH DINITROCHLOROBENZENES [J].

BACALOGLU, R ;

BLASKO, A ;

BUNTON, C ;

DORWIN, E ;

ORTEGA, F ;

ZUCCO, C .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (01) :238-246

← 1 2 3 4 5 6 7 →