Fragmentation reactions of realgar caused by early transition metal hydrides

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• 作者：Walter Meier^a ; Yves Mugnier^b ; Patrick Schwarz^a ; Manfred Scheer^a ; Joachim Wachter^a ; ^{Joachim.Wachter@chemie.uni-regensburg.de} ; Manfred Zabel^a
• 关键词：Arsenic sulfides ; Niobium ; Tantalum ; Coordination compounds
• 刊名：Inorganica Chimica Acta
• 出版年：2012
• 期刊代码：40_00201693
• 类别：ch
• 出版时间：15 May, 2012
• 卷：386
• 期：Complete
• 页码：50-55
• 文件大小：723 K

摘要

The reaction of realgar with [Cp鈥?sub>2MH₃] in boiling toluene gave [Cp鈥?sub>2M₂As₂S₆] (Cp鈥?#xA0;= t-BuC₅H₄; M = Nb: 1; Ta: 2), while [Cp₂WH₂] (Cp = C₅H₅) reacted with As₄S₄ to give [Cp₂W(H)(畏¹-As₅S₂)] (6). The structures were determined by X-ray crystallography. Compounds 1 and 2 are dimers in which two Cp鈥睲 units are symmetrically bridged by a 渭,畏^2:2-AsS₃ ligand, a sulfide ligand and a heteroallylic 渭,畏^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)₅THF gave [Cp鈥?sub>2Nb₂As₂S₆路W(CO)₅] (3) and [Cp鈥?sub>2Nb₂As₂S₆W(CO)₃路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 As₃ 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 = 鈭?.73 V (1), 鈭?.55 V (3) and 鈭?.67 V (4), respectively.