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Energetics of the ruthenium-halide bond in olefin metathesis (pre)catalysts

A DFT analysis of the strength of the Ru-halide bond in a series of typical olefin metathesis (pre)catalysts is presented. The calculated Ru-halide bond energies span the rather broad window of 25-43 kcal mol(-1). This indicates that in many systems dissociation of the Ru-halide bond is possible and is actually competitive with dissociation of the labile ligand generating the 14e active species. Consequently, formation of cationic Ru species in solution should be considered as a possible event

The authors are grateful to the European Commission (FP7 grant CP-FP 211468-2 EUMET and CIG09-GA-2011-293900 to AP), to the Spanish MICINN (Ramon y Cajal contract RYC-2009-05226 to AP) and to the Royal Society (University Research Fellowship to CSJC). LC thanks ENEA (http://www.enea.it) and the HPC team for support as for using the ENEA-GRID and the HPC facilities CRESCO (http://www.cresco.enea.it) Portici (Naples, Italy)

© Dalton Transactions, 2013, vol. 42, núm. 20, p. 7312-7317

Royal Society of Chemistry

Author: Falivene, Laura
Poater Teixidor, Albert
Cazin, Catherine S. J.
Slugovc, Christian
Cavallo, Luigi
Date: 2013
Abstract: A DFT analysis of the strength of the Ru-halide bond in a series of typical olefin metathesis (pre)catalysts is presented. The calculated Ru-halide bond energies span the rather broad window of 25-43 kcal mol(-1). This indicates that in many systems dissociation of the Ru-halide bond is possible and is actually competitive with dissociation of the labile ligand generating the 14e active species. Consequently, formation of cationic Ru species in solution should be considered as a possible event
The authors are grateful to the European Commission (FP7 grant CP-FP 211468-2 EUMET and CIG09-GA-2011-293900 to AP), to the Spanish MICINN (Ramon y Cajal contract RYC-2009-05226 to AP) and to the Royal Society (University Research Fellowship to CSJC). LC thanks ENEA (http://www.enea.it) and the HPC team for support as for using the ENEA-GRID and the HPC facilities CRESCO (http://www.cresco.enea.it) Portici (Naples, Italy)
Format: application/pdf
ISSN: 1477-9226 (versió paper)
1477-9234 (versió electrònica)
Document access: http://hdl.handle.net/10256/8656
Language: eng
Publisher: Royal Society of Chemistry
Collection: MICINN/PN 2012-2015/RYC-2009-05226
Reproducció digital del document publicat a: http://dx.doi.org/10.1039/c2dt32277c
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/293900
Is part of: © Dalton Transactions, 2013, vol. 42, núm. 20, p. 7312-7317
Rights: Tots els drets reservats
Subject: Ruteni -- Compostos
Ruthenium compounds
Catalitzadors
Catalysts
Metàtesi (Química)
Metathesis (Chemistry)
Title: Energetics of the ruthenium-halide bond in olefin metathesis (pre)catalysts
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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