Cycloisomerization and [2+2]cyclodimerization of 1,5-cyclooctadiene catalyzed with the Ni(COD)2/BF3·OEt2 system Научная публикация
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Journal of Molecular Catalysis A: Chemical
ISSN: 1381-1169 |
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| Вых. Данные | Год: 2009, Том: 315, Номер: 2, Страницы: 231-238 Страниц : 8 DOI: 10.1016/j.molcata.2009.09.017 | ||||||
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Реферат:
The catalytic system Ni(COD)2/BF3·OEt2 has been studied in conversions of 1,5-cyclooctadiene under argon and ethylene atmosphere. It has been demonstrated that the catalytic system formed under argon exhibits a high effectiveness in cycloisomerization of 1,5-COD surpassing in this characteristic all known nickel complex catalysts (selectivity to bicyclo-[3.3.0]-octene-2 is up to 99.5% at 100% conversion). In the case of ethylene atmosphere the system produces mainly dimers (yield of cyclodimers above 70%). It has been shown that the catalytic system Ni(COD)2/BF3·OEt2 has the feature of “a living catalyst” consisting in resuming the initial activity with a new portion of 1,5-COD added when the monomer was fully exhausted. The main and side products of the 1,5-COD conversion have been identified with GC-MS and preparative liquid chromatography combined with NMR and IR spectroscopy. Based on EPR and IR spectroscopic data a mechanism for the catalytic performance of the Ni(COD)2/BF3·OEt2 system in argon or ethylene atmospheres is suggested. It has been shown that Ni(0) is oxidized by the Lewis acid to Ni(I) which is stabilized by substrate molecules in a mononuclear form without involvement of conventional organoelement entities. Three sorts of paramagnetic nickel species have been found: ionic complexes containing π-coordinated COD ligands; ionic complexes σ-bonded to COD; complexes as intimate pairs with BF4− counter ions. A mechanism for the catalytic conversion of 1,5-cyclooctadiene is proposed.
Библиографическая ссылка:
Saraev V.V.
, Kraikivskii P.B.
, Matveev D.A.
, Bocharova V.V.
, Petrovskii S.K.
, Zelinskii S.N.
, Vilms A.I.
, Klein H-F.
Cycloisomerization and [2+2]cyclodimerization of 1,5-cyclooctadiene catalyzed with the Ni(COD)2/BF3·OEt2 system
Journal of Molecular Catalysis A: Chemical. 2009. V.315. N2. P.231-238. DOI: 10.1016/j.molcata.2009.09.017 WOS Scopus РИНЦ OpenAlex
Cycloisomerization and [2+2]cyclodimerization of 1,5-cyclooctadiene catalyzed with the Ni(COD)2/BF3·OEt2 system
Journal of Molecular Catalysis A: Chemical. 2009. V.315. N2. P.231-238. DOI: 10.1016/j.molcata.2009.09.017 WOS Scopus РИНЦ OpenAlex
Идентификаторы БД:
| Web of science: | WOS:000272561300015 |
| Scopus: | 2-s2.0-71649114304 |
| РИНЦ: | 15313020 |
| OpenAlex: | W2052952151 |