Reaction of sodium amalgam with (μ-enyne)bis(dicarbonyl-η5-cyclopentadienylmolybdenum(I)) and (μ-η2,η3-allenyl)bis(dicarbonyl-η5-cyclopentadienylmolybdenum) tetrafluoroborate complexes. Crystal structure of [[{MO(η5-C5H5)(CO)22}2{μ-HCCCH(CH2CH3)}]2]
| Autor: | Jean-François Capon, Rene Kergoat, Roger Pichon, Paul L'Haridon, N. Le Berre-Cosquer, S. Cornen |
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| Rok vydání: | 1994 |
| Předmět: |
chemistry.chemical_classification
Allylic rearrangement Tetrafluoroborate Enyne Stereochemistry Organic Chemistry Alkyne Protonation Crystal structure Biochemistry Medicinal chemistry Sodium amalgam Inorganic Chemistry chemistry.chemical_compound chemistry Vinylacetylene Materials Chemistry Physical and Theoretical Chemistry |
| Zdroj: | Journal of Organometallic Chemistry. 470:137-145 |
| ISSN: | 0022-328X |
| DOI: | 10.1016/0022-328x(94)80158-4 |
| Popis: | The behaviour of μ-enyne complexes [CP2MO2(CO)4(μ-HCCR)] [CP2MO2(CO)4 [Mo(η5-C5H5)(CO)2]2; R C(CH3)CH2 (1); R CHCHCH3 (2;) R C6H9 (3)] and of the corresponding μ-η2,η3-allenyl [Cp2Mo2(CO)4(μ-η2,η3-HCCR′)][BF4] [R′ C(CH3)2 (4); R′ CHCH2CH3 (5); R′ C6H10 (6)] towards Na/Hg has been studied and compared with that of the vinylacetylene and protonated vinylacetylene species [Cp2Mo2(CO)4(μ-HCCCHCH2)] (11) and [Cp2Mo2(CO)4(μ-η2,η3 -HCCCHCH3)]-[BF4] (14), respectively. It appears that when the Cγ carbon atom of the μ-enyne bears a hydrogen atom (complexes 2 and 11), dimerization occurs leading to tetrametallic species [[{Cp2Mo2(CO)4}(μ-HCCCH2CHCH3)]2] (8) and [[{Cp2Mo2(CO)4}(μ-HCCCH2CH2)]2] (12). In the other cases, μ-σ,η3 allylic species such as [Cp2Mo2(CO)4 {μ-σ,η3-HC ⋯ CH ⋯ C(CH3)2}] (7) are formed. Reaction of Na/Hg with most of the μ-η2,η3 allenyl complexes regenerates the parent μ-enyne compounds. When the “C+” carbon atom bears a hydrogen atom, carbon-carbon coupling leading to a dimerization is favoured. The crystal structure of tetrametallic [[{Cp2Mo2(CO)4}{μ-HCCCH(CH2CH3)}]2] (10) obtained from 5 has been determined. |
| Databáze: | OpenAIRE |
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