Unique solubility of polyoxoniobate salts in methanol: coordination to cations and POM methylation
| Autor: | N. B. Kompankov, Maxim N. Sokolov, Cristian Vicent, J. A. Laricheva, Pavel A. Abramov |
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| Rok vydání: | 2016 |
| Předmět: |
010405 organic chemistry
General Chemical Engineering Chemical shift media_common.quotation_subject Inorganic chemistry General Chemistry Methylation Carbon-13 NMR 010402 general chemistry 01 natural sciences Relative stability 0104 chemical sciences Sodium salt chemistry.chemical_compound Speciation chemistry Methanol Solubility media_common |
| Zdroj: | RSC Advances. 6:20240-20246 |
| ISSN: | 2046-2069 |
| Popis: | Sodium salts of hybrid organometallic POM complexes consisting of [M6O19]8− (M = Nb, Ta) and half-sandwich fragments {Cp*M}2+ (Cp* = η5-C5(CH3)5; M = Rh, Ir) and {(C6H6)Ru}2+ dissolve only in one organic solvent, that is, in methanol. From methanolic solutions, crystals of Na4[trans-{(C6H6)Ru}2Nb6O19]·14.125MeOH·2H2O (1), K4[trans-{Cp*Rh}2Nb6O19]·4MeOH·10H2O (2) and K4[trans-{Cp*Ir}2Nb6O19]·10MeOH·4H2O (3) were isolated and characterized by X-ray analysis. Methoxo species [{LM′}2M6O19−n(OCH3)n] (n = 1–3) were detected in solution by ESI-MS and NMR, and they account only for about half of the total speciation in the solution. DFT calculations were used to calculate 13C NMR chemical shifts in the methoxo complexes and to assess their relative stability. Reasons for the preferred solubility in methanol are discussed. |
| Databáze: | OpenAIRE |
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