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Computational study of productive and non-productive cycles in fluoroalkene metathesis.

ABSTRACT: A detailed DFT study of the mechanism of metathesis of fluoroethene, 1-fluoroethene, 1,1-difluoroethene, cis- and trans-1,2-difluoroethene, tetrafluoroethene and chlorotrifluoroethene catalysed with the Hoveyda-Grubbs 2(nd) generation catalyst was performed. It revealed that a successful metathesis of hydrofluoroethenes is hampered by a high preference for a non-productive catalytic cycle proceeding through a ruthenacyclobutane intermediate bearing fluorines in positions 2 and 4. Moreover, the calculations showed that the cross-metathesis of perfluoro- or perhaloalkenes should be a feasible process and that the metathesis is not very sensitive to stereochemical issues.

SUBMITTER: Rybackova M

PROVIDER: S-EPMC4660995 | biostudies-literature | 2015

REPOSITORIES: biostudies-literature

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Computational study of productive and non-productive cycles in fluoroalkene metathesis.

Rybáčková Markéta M Hošek Jan J Šimůnek Ondřej O Kolaříková Viola V Kvíčala Jaroslav J

Beilstein journal of organic chemistry 20151110

A detailed DFT study of the mechanism of metathesis of fluoroethene, 1-fluoroethene, 1,1-difluoroethene, cis- and trans-1,2-difluoroethene, tetrafluoroethene and chlorotrifluoroethene catalysed with the Hoveyda-Grubbs 2(nd) generation catalyst was performed. It revealed that a successful metathesis of hydrofluoroethenes is hampered by a high preference for a non-productive catalytic cycle proceeding through a ruthenacyclobutane intermediate bearing fluorines in positions 2 and 4. Moreover, the c ...[more]

PMID: 26664636

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