Meier, Walter and Mugnier, Yves and Schwarz, Patrick and Scheer, Manfred and Wachter, Joachim and Zabel, Manfred (2012) Fragmentation reactions of realgar caused by early transition metal hydrides. INORGANICA CHIMICA ACTA, 386. pp. 50-55. ISSN 0020-1693,
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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.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | GROUP 15/16 ELEMENTS; ORGANOMETALLIC COMPLEXES; COORDINATION CHEMISTRY; CRYSTAL-STRUCTURE; LIGAND COMPLEXES; CAGE STRUCTURES; AS4S4; CP-ASTERISK=C5ME5; DERIVATIVES; MOLYBDENUM; Arsenic sulfides; Niobium; Tantalum; Coordination compounds |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 14 May 2020 05:07 |
| Last Modified: | 14 May 2020 05:07 |
| URI: | https://pred.uni-regensburg.de/id/eprint/18743 |
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