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Titolo:
Application of capillary electrophoresis to stereochemical conversions. A case study: the photoracemization/hydrolysis of Cr(diimine)(3)(3+) species
Autore:
Mytykh, OV; Martin, SE; Wheeler, JF; Kane-Maguire, NAP;
Indirizzi:
Furman Univ, Dept Chem, Greenville, SC 29613 USA Furman Univ Greenville SC USA 29613 , Dept Chem, Greenville, SC 29613 USA
Titolo Testata:
INORGANICA CHIMICA ACTA
fascicolo: 1-2, volume: 311, anno: 2000,
pagine: 143 - 146
SICI:
0020-1693(200012)311:1-2<143:AOCETS>2.0.ZU;2-0
Fonte:
ISI
Lingua:
ENG
Soggetto:
ALKALINE AQUEOUS-MEDIA; TRIS(1,10-PHENANTHROLINE)CHROMIUM(III) ION; COMPLEXES;
Keywords:
capillary electrophoresis; chromium complexes; photohydrolysis; photoracemization;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
23
Recensione:
Indirizzi per estratti:
Indirizzo: Wheeler, JF Furman Univ, Dept Chem, Greenville, SC 29613 USA Furman Univ Greenville SC USA 29613 Greenville, SC 29613 USA
Citazione:
O.V. Mytykh et al., "Application of capillary electrophoresis to stereochemical conversions. A case study: the photoracemization/hydrolysis of Cr(diimine)(3)(3+) species", INORG CHIM, 311(1-2), 2000, pp. 143-146

Abstract

Capillary electrophoresis (CE) is shown to be a powerful probe of the stereochemical changes accompanying photoinitiated racemization and ligand substitution of optically active Cr(diimine)(3)(3+) complexes (diimine = 2,2'-bipyridine or 1,10-phenanthroline) in aqueous solution. With dibenzoyl-L-tartrate as a chiral additive in the CE capillary buffer, the electropherograms of photolyzed samples of Lambda -Cr(diimine)(3)(3+) species display excellent separations of the Lambda and Delta optical isomers of both the parentCr(diimine),3+ complex and the hydrolysis products. Therefore, we have utilized CE analysis as a direct probe of the extent of racemization of the parent Lambda -Cr(diimine)(3)(3+) complexes, while simultaneously determiningthe optical purity of the hydrolysis product. For pH 2 irradiations, racemization of both Cr(diimine)(3)(3+) complexes proceeds without concomitant cis-Cr(diimine)(2)(H2O)(2)(3+) formation. The corresponding data at pH 7.4 reveal that racemization and hydrolysis are concurrent processes, with formation of the hydrolysis product proceeding with complete loss of optical configuration. For photolyses at pH 11.6, extensive base hydrolysis is apparent (again with no retention of absolute configuration), but is accompanied by the absence of direct Lambda -Cr(diimine)(3)(3+) racemization. These results provide support for racemization and hydrolysis proceeding via a commonintermediate. (C) 2000 Elsevier Science B.V. All rights reserved.

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Documento generato il 27/01/20 alle ore 07:16:24