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Cycloisomerization and [2 + 2]cyclodimerization of 1,5-cyclooctadiene catalyzed with the Ni(COD)2/BF3·OEt2 system. / Saraev, V. V.; Kraikivskii, P. B.; Matveev, D. A.; Bocharova, V. V.; Petrovskii, S. K.; Zelinskii, S. N.; Vilms, A. I.; Klein, Hans Friedrich.

In: Journal of Molecular Catalysis A: Chemical, Vol. 315, No. 2, 15.01.2010, p. 231-238.

Research output: Contribution to journal › Article › peer-review

Harvard

Saraev, VV, Kraikivskii, PB, Matveev, DA, Bocharova, VV, Petrovskii, SK, Zelinskii, SN, Vilms, AI & Klein, HF 2010, 'Cycloisomerization and [2 + 2]cyclodimerization of 1,5-cyclooctadiene catalyzed with the Ni(COD)2/BF3·OEt2 system', Journal of Molecular Catalysis A: Chemical, vol. 315, no. 2, pp. 231-238. https://doi.org/10.1016/j.molcata.2009.09.017

APA

Saraev, V. V., Kraikivskii, P. B., Matveev, D. A., Bocharova, V. V., Petrovskii, S. K., Zelinskii, S. N., Vilms, A. I., & Klein, H. F. (2010). Cycloisomerization and [2 + 2]cyclodimerization of 1,5-cyclooctadiene catalyzed with the Ni(COD)2/BF3·OEt2 system. Journal of Molecular Catalysis A: Chemical, 315(2), 231-238. https://doi.org/10.1016/j.molcata.2009.09.017

Vancouver

Saraev VV, Kraikivskii PB, Matveev DA, Bocharova VV, Petrovskii SK, Zelinskii SN et al. Cycloisomerization and [2 + 2]cyclodimerization of 1,5-cyclooctadiene catalyzed with the Ni(COD)2/BF3·OEt2 system. Journal of Molecular Catalysis A: Chemical. 2010 Jan 15;315(2):231-238. https://doi.org/10.1016/j.molcata.2009.09.017

Author

Saraev, V. V. ; Kraikivskii, P. B. ; Matveev, D. A. ; Bocharova, V. V. ; Petrovskii, S. K. ; Zelinskii, S. N. ; Vilms, A. I. ; Klein, Hans Friedrich. / Cycloisomerization and [2 + 2]cyclodimerization of 1,5-cyclooctadiene catalyzed with the Ni(COD)2/BF3·OEt2 system. In: Journal of Molecular Catalysis A: Chemical. 2010 ; Vol. 315, No. 2. pp. 231-238.

BibTeX

@article{8d55ac3ddc7d4ca2828db4e2b301339e,
title = "Cycloisomerization and [2 + 2]cyclodimerization of 1,5-cyclooctadiene catalyzed with the Ni(COD)2/BF3·OEt2 system",
abstract = "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.",
keywords = "1,5-Cyclooctadiene, Cyclodimerization, Cycloisomerization, Mechanism, Nickel(I)",
author = "Saraev, {V. V.} and Kraikivskii, {P. B.} and Matveev, {D. A.} and Bocharova, {V. V.} and Petrovskii, {S. K.} and Zelinskii, {S. N.} and Vilms, {A. I.} and Klein, {Hans Friedrich}",
year = "2010",
month = jan,
day = "15",
doi = "10.1016/j.molcata.2009.09.017",
language = "English",
volume = "315",
pages = "231--238",
journal = "Journal of Molecular Catalysis A: Chemical",
issn = "1381-1169",
publisher = "Elsevier",
number = "2",

}

RIS

TY - JOUR

T1 - Cycloisomerization and [2 + 2]cyclodimerization of 1,5-cyclooctadiene catalyzed with the Ni(COD)2/BF3·OEt2 system

AU - Saraev, V. V.

AU - Kraikivskii, P. B.

AU - Matveev, D. A.

AU - Bocharova, V. V.

AU - Petrovskii, S. K.

AU - Zelinskii, S. N.

AU - Vilms, A. I.

AU - Klein, Hans Friedrich

PY - 2010/1/15

Y1 - 2010/1/15

N2 - 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.

AB - 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.

KW - 1,5-Cyclooctadiene

KW - Cyclodimerization

KW - Cycloisomerization

KW - Mechanism

KW - Nickel(I)

UR - http://www.scopus.com/inward/record.url?scp=71649114304&partnerID=8YFLogxK

U2 - 10.1016/j.molcata.2009.09.017

DO - 10.1016/j.molcata.2009.09.017

M3 - Article

AN - SCOPUS:71649114304

VL - 315

SP - 231

EP - 238

JO - Journal of Molecular Catalysis A: Chemical

JF - Journal of Molecular Catalysis A: Chemical

SN - 1381-1169

IS - 2

ER -

ID: 51891745