From Solid State to Solution: Advancing Chemistry of Bi鈥揃i and Bi鈥揜h Paddlewheel Carboxylates

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• 作者：Alexander S. Filatov ; Margaret Napier ; Volodimir D. Vreshch ; Natalie J. Sumner ; Evgeny V. Dikarev ; Marina A. Petrukhina
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：January 2, 2012
• 年：2012
• 卷：51
• 期：1
• 页码：566-571
• 全文大小：288K
• 年卷期：v.51,no.1(January 2, 2012)
• ISSN：1520-510X

文摘

The first successful high-yield solution synthesis of homobimetallic Bi₂(O₂CCF₃)₄ (1), as well as heterobimetallic BiRh(O₂CCF₃)₄ (2) and BiRh(O₂CCF₂CF₃)₄ (3), complexes is reported. It is based on one-pot reduction reactions starting from Bi(III) and Rh(II) carboxylates and using Bi metal as a reducing agent. The presence of small amounts of diphenyl ether was found to facilitate this reaction, most probably because of its good solubilizing and 蟺-stabilizing abilities. The latter is illustrated by the isolation and structural characterization of a 蟺-adduct of 1 with diphenyl ether, [Bi₂(O₂CCF₃)₄路1/2Ph₂O]. Importantly, the new approach expands to solution the chemistry of Bi(II) that was previously limited to the solid state only. The solution procedure developed for the preparation of heterometallic BiRh(O₂CCF₃)₄ is now one step shorter and gives the product in excellent yield compared with the previously reported method based on sublimation-deposition technique. It is also performed on a greater scale (10鈥?0 times) and makes further scale-up feasible, if needed. Moreover, it eliminates the isolation of the hard-to-handle unsolvated Bi(II) trifluoroacetate used earlier as a starting material. A new polymorph of BiRh(O₂CCF₃)₄ (2) was crystallized from solution in this work. The solution approach was also applied to the synthesis of a new heterobimetallic carboxylate with perfluorinated propionate ligands, BiRh(O₂CCF₂CF₃)₄ (3). All products are fully characterized by spectroscopic and single crystal X-ray diffraction methods. Complexes 2 and 3 exhibit similar solid state structures based on heterobimetallic paddlewheel units forming infinite 1D chains through intermolecular Rh路路路O interactions.