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Titolo:
THE STEREOCHEMISTRY OF THE OXIDATION OF DIAMINES AND OF THE REDUCTIONOF DIIMINES IN THE COORDINATION SPHERE OF RUTHENIUM(II)
Autore:
JANDRASICS E; KOLP B; WOLNY JA; VONZELEWSKY A;
Indirizzi:
UNIV FRIBOURG,INST INORGAN CHEM,PEROLLES CH-1700 FRIBOURG SWITZERLAND UNIV FRIBOURG,INST INORGAN CHEM CH-1700 FRIBOURG SWITZERLAND UNIV WROCLAW,FAC CHEM PL-50370 WROCLAW POLAND
Titolo Testata:
Inorganica Chimica Acta
fascicolo: 1-2, volume: 272, anno: 1998,
pagine: 153 - 161
SICI:
0020-1693(1998)272:1-2<153:TSOTOO>2.0.ZU;2-K
Fonte:
ISI
Lingua:
ENG
Soggetto:
ASYMMETRIC HYDROGENATION; DEHYDROGENATION; IMINES; CATALYSTS; AMINES; DISPROPORTIONATION; COMPLEXES; MECHANISM; ATOM;
Keywords:
STEREOSPECIFIC OXIDATION; STEREOSPECIFIC REDUCTION; RUTHENIUM COMPLEXES; BIPYRIDINE COMPLEXES; DIAMINES; DIIMINES;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Science Citation Index Expanded
Citazioni:
30
Recensione:
Indirizzi per estratti:
Citazione:
E. Jandrasics et al., "THE STEREOCHEMISTRY OF THE OXIDATION OF DIAMINES AND OF THE REDUCTIONOF DIIMINES IN THE COORDINATION SPHERE OF RUTHENIUM(II)", Inorganica Chimica Acta, 272(1-2), 1998, pp. 153-161

Abstract

The syntheses of Delta/Lambda-, Delta-, and Lambda-[Ru(bpy)(2)(1R,2R-chxn)](2+) (where 1R,2R-chxn=(1R,2R)-(-)-1,2-diaminocyclohexane); rac.-, Delta-, and Lambda-[Ru(bpy)(2)(chxdiim](2+) (where chxdiim=1,2-diiminocyclohexane); rac.-, and Delta-[Ru(bpy)(2)(dmen)](2+) (where dmen=N,N'-(dimethyl)ethylenediamine), and rac.-, and Delta-[Ru(bpy)(2)(dmdiim)](2+) (where dmdiim=N,N'-(dimethyl)ethylenediimine) are described. Oxidation of the coordinated diamines with an acid solution of Ce(IV) and reduction of the coordinated diimines with NaBD4 occur under retention of the configuration at the metal center. Reduction of the diiminecomplexes with NaBD4 gives back the amines with a diastereomeric excess (Lambda-R,R and Delta-S,S) of 60% in case of chxn as a ligand and 80% for the dmen ligand. The latter becomes a chiral ligand upon deuteration. The reduction also yields a small amount cup to 10%) of the corresponding cis isomers (Delta-R,S/Lambda-S,R). In addition, semi-reduced coordinated amine/imine ligands are observed as intermediates. The identity of the reaction products as well as their configurations has been established by means of circular dichroism and H-1 NMR spectroscopy. (C) 1998 Elsevier Science S.A. All rights reserved.

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Documento generato il 21/09/20 alle ore 05:07:32