Zusammenfassung
The reaction of realgar with [Cp'2MH3] in boiling toluene gave [Cp'2M2As2S6] (Cp' = t-BuC5H4; M = Nb: 1; Ta: 2), while [Cp2WH2] (Cp = C5H5) reacted with As4S4 to give [Cp2W(H)(eta(1)-As5S2)] (6). The structures were determined by X-ray crystallography. Compounds 1 and 2 are dimers in which two Cp'M units are symmetrically bridged by a mu, eta(2:2)-AsS3 ligand, a sulfide ligand and a heteroallylic ...
Zusammenfassung
The reaction of realgar with [Cp'2MH3] in boiling toluene gave [Cp'2M2As2S6] (Cp' = t-BuC5H4; M = Nb: 1; Ta: 2), while [Cp2WH2] (Cp = C5H5) reacted with As4S4 to give [Cp2W(H)(eta(1)-As5S2)] (6). The structures were determined by X-ray crystallography. Compounds 1 and 2 are dimers in which two Cp'M units are symmetrically bridged by a mu, eta(2:2)-AsS3 ligand, a sulfide ligand and a heteroallylic mu, eta(2:2)-AsS2 ligand. The structure of 6 belongs to the type of bent metallocenes in which tungsten is surrounded tetrahedrally by two Cp ligands, a crystallographically found hydride atom and the new As5S2 cage. The reaction of 1 with W(CO)(5)THF gave [Cp'2Nb2As2S6 center dot W(CO)(5)] (3) and [Cp'2Nb2As2S6W(CO)(3)center dot W(CO)(5)] (4). Compound 3 is a monoadduct of 1 bearing the W(CO)5 fragment at the As atom of the AsS3 ligand. The structure of 4 contains a distorted cubane-like Nb2WS4As cluster with an integrated W(CO) 3 unit. A similar cluster 5 containing a CuI fragment instead of W(CO) 3 was prepared from 1 and CuI. The structure is completed by an attached As4S3 cage, the As-3 basis of which is oriented towards iodide. Electrochemical investigations of 1, 3, and 4 shows for each compound quasi-reversible one-electron reductions with E-1/2 = -0.73 V (1), -0.55 V (3) and -0.67 V (4), respectively. (C) 2012 Elsevier B. V. All rights reserved.
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