ISSN:
0044-2313
Keywords:
Ethene-1,2-dithiolate and -diselenolate chelate ligands
;
halfsandwich rhenium complexes
;
oligochalcogenide complexes
;
dimethyl acetylene dicarboxylate
;
crystal structures
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Reactions of Halfsandwich Rhenium(V) Oligochalcogenide Complexes with Dimethyl Acetylene Dicarboxylate. Molecular Structures of the New 1,2-Dicarbomethoxy-ethene-1,2-dichalcogenate Chelate Compounds Cp*Re[S2C2(COOMe)2]2 and Cp*Re(NtBu)[Se2C2(COOMe)2]The reaction of Cp*Re(S3)(S4) (1a) with dimethyl acetylene dicarboxylate (dmad) leads through the blue intermediate Cp*Re(S4)[S2C2(COOMe)2] (2a) to the red bis(ethene-1,2-dithiolato) complex Cp*Re[S2C2(COOMe)2]2 (3a). The product 3a is also formed in the reactions of dmad with the tetrasulfidorhenium complexes Cp*Re(L)(S4) (L = O (4a), NtBu (5a)) while the analogous tetraselenidorhenium compounds Cp*Re(L)(Se4) (4b and 5b) are only transformed to Cp*Re(L)[Se2C2(COOMe)2] (L = O (6b), NtBu (7b)). According to the X-ray crystal structure analyses, the (ethene-1,2-dithiolato)rhenium chelate rings in 3a are folded along the S … S vector towards the Cp* ligand (angle between the planes ReS2/S2C2 159.2°), whereas the ReSe2C2 chelate ring in 7b is planar.
Notes:
Inhaltsübersicht.(1) Bei der Umsetzung von Cp*Re(S3)(S4) (1a) mit Acetylen-dicarbonsäuredimethylester (dmad) entsteht über die blaue Zwischenstufe Cp*Re(S4)[S2C2(COOMe)2] (2a) hinweg der rote Bis(ethen-1,2-dithiolato)-Komplex Cp*Re[S2C2(COOMe)2]2 (3a). Auch die Tetrasulfidorhenium-Komplexe Cp*Re(L)(S4) (L = O (4a), NtBu (5a)) ergeben mit dmad das Produkt 3a, während die analogen Tetraselenidorhenium-Verbindungen Cp*Re(L)(Se4) (4b und 5b) nur zu Cp*Re(L)[Se2C2(COOMe)2] (L = O (6b), NtBu (7b)) umgesetzt werden. Nach den Röntgenstrukturanalysen sind die Ethen-1,2-dithiolato-rhenium-Chelatringe in 3a entlang des S … S Vektors zum Cp*-Liganden hin abgeknickt (Winkel zwischen den Ebenen ReS2/S2C2 159,2°), während der ReSe2C2 Chelatring in 7b eben ist.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19946200725
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