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Simple and cheap steric and electronic characterization of the reactivity of Ru(II) complexes containing oxazoline ligands as epoxidation catalysts

The reactivity of a new family of complexes with general formula [Ru-IV(T)(R-D)(O)](2+) (T = trispyrazolylmethane (tpm); D = N-(1-hydroxy-3-methylbutan-(2S)-(-)-2-yl)-(4S)-(-)-4-isopropyl-4,5-dihydrooxazole-2-carbimidate, R = Bz (1); iPr (2)) has been analyzed. There is a significant difference in regioselectivity between the two catalysts in the epoxidation of 4-vinylcyclohexene; 1 leads to the regioselective oxidation at the ring alkene position, whereas 2 leads to the oxidation at the terminal position. Although computational calculations indicate small energy differences, both the geometry through steric maps and the electronic parameters of the reactants via conceptual DFT, or charges via NPA, explain the reactivity differences found for the catalysts depending on the substituents of the oxazoline ligands

We acknowledge financial support from the MICINN of Spain (CTQ2007-60476/PPQ to I. R and M. R. and CTQ2011-23156/BQU to M. S.), the DIUE of the Generalitat de Catalunya (projects 2009SGR637 and Xarxa de Referencia en Quimica Teorica i Computacional), and the European Fund for Regional Development fund for the grant UNGI08-4E-003. M. S. is also grateful to the DIUE of the Generalitat de Catalunya for financial help through the ICREA Academia 2009 prize for excellence in research. A. P. thanks MICINN for a Ramon y Cajal contract (RYC-2009-05226), European Commission for a Career Integration Grant (CIG09-GA-2011-293900), and Generalitat de Catalunya (2012BE100824)

© Chemical Physics Letters, 2013, vol. 577, p. 142-146

Elsevier

Author: Poater Teixidor, Albert
Falivene, Laura
Cavallo, Luigi
Llobet Dalmases, Antoni
Rodríguez Pizarro, Montserrat
Romero García, Isabel
Solà i Puig, Miquel
Date: 2013
Abstract: The reactivity of a new family of complexes with general formula [Ru-IV(T)(R-D)(O)](2+) (T = trispyrazolylmethane (tpm); D = N-(1-hydroxy-3-methylbutan-(2S)-(-)-2-yl)-(4S)-(-)-4-isopropyl-4,5-dihydrooxazole-2-carbimidate, R = Bz (1); iPr (2)) has been analyzed. There is a significant difference in regioselectivity between the two catalysts in the epoxidation of 4-vinylcyclohexene; 1 leads to the regioselective oxidation at the ring alkene position, whereas 2 leads to the oxidation at the terminal position. Although computational calculations indicate small energy differences, both the geometry through steric maps and the electronic parameters of the reactants via conceptual DFT, or charges via NPA, explain the reactivity differences found for the catalysts depending on the substituents of the oxazoline ligands
We acknowledge financial support from the MICINN of Spain (CTQ2007-60476/PPQ to I. R and M. R. and CTQ2011-23156/BQU to M. S.), the DIUE of the Generalitat de Catalunya (projects 2009SGR637 and Xarxa de Referencia en Quimica Teorica i Computacional), and the European Fund for Regional Development fund for the grant UNGI08-4E-003. M. S. is also grateful to the DIUE of the Generalitat de Catalunya for financial help through the ICREA Academia 2009 prize for excellence in research. A. P. thanks MICINN for a Ramon y Cajal contract (RYC-2009-05226), European Commission for a Career Integration Grant (CIG09-GA-2011-293900), and Generalitat de Catalunya (2012BE100824)
Format: application/pdf
ISSN: 0009-2614
Document access: http://hdl.handle.net/10256/8648
Language: eng
Publisher: Elsevier
Collection: MEC/PN 2007-2010/CTQ2007-60476/PPQ
MICINN/PN 2012-2014/CTQ2011-23156
AGAUR/2009-2014/2009 SGR-637
MICINN/PN 2012-2015/RYC-2009-05226
AGAUR/2012BE100824
Reproducció digital del document publicat a: http://dx.doi.org/10.1016/j.cplett.2013.05.032
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/293900
Is part of: © Chemical Physics Letters, 2013, vol. 577, p. 142-146
Rights: Tots els drets reservats
Subject: Catàlisi asimètrica
Enantioselective catalysis
Compostos heterocíclics
Heterocyclic compounds
Ruteni -- Compostos
Ruthenium compounds
Title: Simple and cheap steric and electronic characterization of the reactivity of Ru(II) complexes containing oxazoline ligands as epoxidation catalysts
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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