ISSN:
0044-2313
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Electrochemical Reduction of CSSe and CSe2 in Dimethylformamide: Heterocyclic 1,2-Dichalcogenolates and their Coordination ChemistryStarting from carbon diselenide or carbon selenidesulfide the electrochemical preparation (electrosynthesis) of heterocyclic dichalcogenolates C3X52- (X = Se: dsis; X = S/Se: C3SxSey2-) is outlined. The 1,2-dichalcogenolate compounds were isolated and characterized as dibenzoyl derivatives. Bis- or tris-chelates of general type Am[M(C3X5)n] (with A = Bu4N+, Ph4As+; M = ZnII, PtII, PdII, NiIII, CuIII, AuIII, InIII; X = Se, S/Se; m = 1, 2, 3; n = 2, 3, respectively) are available directly from methanolic solutions of the dibenzoylates after hydrolytic cleavage of the latter with sodium methanolate. In addition bis-chelates Bu4N[Ni(C3X5)2] (X = Se, S/Se) have been characterized by cyclovoltammetry and epr spectroscopy and compared with the corresponding all-sulfur ligand compound Bu4N[Ni(dmit)2] (X = S). Arguments are given for the fact that the allselenium ligand dsis (X = Se) yields the CuIII or NiIII chelate at once whereas with dmit using identical conditions the metal(II) compounds are formed.
Notes:
Ausgehend von Selenkohlenstoff und Selenschwefelkohlenstoff wird die elektrochemische Darstellung heterocyclischer Dichalkogenolate C3X52- (X = Se: dsis; X = S/Se: C3SxSey2-), die als Dibenzoylverbindungen isoliert und charakterisiert werden, beschrieben. Aus den mit Alkalimethanolat erhaltenen Verseifungslösungen dieser Dibenzoylverbindungen sind Metall-bis- und -tris-Chelate der heterocyclischen 1, 2-Dichalkogenolate vom Typ Am[M(C3X5)n] (A = Bu4N+, Ph4As+; M = ZnII, PtII, PdII, NiIII, CuIII, AuIII, InIII; X = Se, S/Se; m = 1, 2, 3; n = 2, 3) unmittelbar zugänglich. Cyclovoltammetrisch und mittels EPR werden die Nickel(III)-Verbindungen Bu4N[Ni(C3X5)2] (X = Se, S/Se) charakterisiert und der analogen Schwefelverbindung Bu4N[Ni(dmit)2] (X = S) gegenübergestellt. Für die bei der Chelatisierung mit dsis (X = Se) beobachtete Metall(II)-Metall(III)-Oxydation bei Kupfer und Nickel werden Argumente erörtert.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19875440121
