ISSN:
0044-2313
Keywords:
Metal(II), -(III) bis-chelates (Bu4N)n[M-(dsise)2]
;
(dsise) — 1,3-dithiole-2-selone-4,5-diselenolate
;
i. r., 13C n.m.r., e.p.r., cyclovoltammetric data
;
ab-initio SCF calculations
;
crystal structure
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Coordination Chemistry of 1,3-Dithiole-2-selone-4,5-diselenolate (dsise) and 1,3-Dithiole-2-selone-4,5-dithiolate (dmise). Crystal and Molecular Structure of Tetrabutylammonium bis(1,3-dithiole-2-selone-4,5-diselenolato)nickelate(II) and -(III), [(n-C4H9)4N]2[Ni(dsise)2 and (n-C4H9)4[Ni(dsise)2]Syntheses and properties of metal(II) and metal(III) bis-chelates of 1,3-dithiole-2-selone-4,5-diselenolate (dsise), of the general type (Bu4N)n)M(dsise)2] (n =2 : M = Zn, Cd, Hg, Cu, Ni, Pd; n = 1: M = Ni, Au) are reported and compared with chelates of the isologue 1,3-dichalcogenole-2-chalcogenoe-4,5-dichalcogenolate (i. r., 13C-n. m. r., e. p. r., cyclovoltammetric data). The unexpected rearrangement during the syntheses of dsise and 1,3-dithiole-2-selone-4,5-diselenolate (dmise) is characterized by ab-initio SCF calculations. The x-ray structures of (Bu4N)2[Ni(dsise)2] (space group P21/c, a = 8.5556(13) Å, b = 15.0009(12) Å, c = 19.696(3) Å, β = 96.018(7)°, V = 2513.9(5) Å3, Z = 2) and Bu4N[Ni(dsise)2] (space group C2/c, a = 25.133(6) Å, b = 9.828(4) Å, c = 18.104(7) Å, β = 132.81(1)°, V = 3281(2) Å3, Z = 4) are given.
Notes:
Synthese und Eigenschaften von Metall(II) und Metall(III) Bis-Chelaten des 1,3-Dithiol-2-selon-4,5-diselenolats (dsise) vom Typ (Bu4N)n[M(dsise)2](n = 2: M = Zn, Cd, Hg, Cu, Ni, Pd; n = 1:M = Ni, Au) werden beschrieben und im Vergleich mit isologen 1,3-Dichalkogenol-2-chalkogenon-4,5-dichalkogenolat-Chelaten diskutiert (IR, 13C-NMR, EPR, Cyclovoltammetrie). Anhand von ab-initio-SCF-Rechnungen wird die bei der Synthese des dsise und des 1,3-Dithiol-2-selon-4,5-dithiolats (dmise) auftretende „Umlagerung“ charakterisiert. Die röntgenkristallographischen Daten von (Bu4N)2[Ni(dsise)2] (Raumgruppe P21/c, a = 8,5556(13) Å, b = 15,0009(12) Å, c = 19,696(3) Å, β = 96,018(7)°, V = 2513,9(5) Å3, (Z = 2) und von Bu4N[Ni(dsise)2] (Raumgruppe C2/c, a = 25,133(6) Å, b = 9,828(4) Å, c = 18,104(7) Å, β = 132,81(1)°, V = 3281(2) Å3, Z = 4) werden vorgestellt.
Additional Material:
7 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19926090320
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