Transformation of Chlorohydrocarbons and Amines in the Coordination Sphere of [(µ‐H) 2 Os 3 (CO) 10 ]
| Autor: | B. Yu. Savkov, A. V. Golovin, A. V. Virovets, Vladimir S. Korenev, M. Yu. Afonin, Vladimir A. Maksakov |
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| Rok vydání: | 2017 |
| Předmět: |
Coordination sphere
010405 organic chemistry Metal carbonyl 010402 general chemistry Photochemistry 01 natural sciences Medicinal chemistry 0104 chemical sciences Inorganic Chemistry chemistry.chemical_compound Deprotonation chemistry Halogen Nucleophilic substitution SN2 reaction Methylene Bond cleavage |
| Zdroj: | European Journal of Inorganic Chemistry. 2017:3105-3114 |
| ISSN: | 1099-0682 1434-1948 |
| Popis: | A reaction has been found and investigated that demonstrates the potential for coordination, activation and transformation of three organic molecules, namely, two methylene chloride molecules and one amine molecule, in the coordination sphere of the [(μ-H)Os3(CO)10]- carbonylate anion, which is formed in situ from the deprotonation of [(μ-H)2Os3(CO)10]. This reaction is very intricate and comprises such steps as the nucleophilic substitution of chloride ions by cluster carbonylate anions in halocarbons, C-H, C-N and C-Cl bond cleavage and C-C and C-N bond formation under unusually mild conditions for such reactions, which leads to the formation of -CH=CH2 or -CH=CHNR2 ligands in [(μ-Cl))Os3(µ2-σ,π-CH=CH2)(СО)10] and [(μ-H)Os3(μ-CH=CHNR2)(CO)10]. The reaction is sensitive to the nature of the halogen in the halocarbons. When bromine or iodine is used in place of chlorine in halohydrocarbons, [(μ-H)Os3(μ-X)(CO)10] (X = Br, I) clusters with good yield are obtained, which apparently indicates a replacement of the SN2 mechanism by SN2Hal. |
| Databáze: | OpenAIRE |
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