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

Albert Poater; Laura Falivene; Luigi Cavallo; Antoni A. Llobet; Montserrat Carmen Ríos Rodríguez; Isabel Romero; Miquel Solà

doi:10.1016/j.cplett.2013.05.032

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

Albert Poater, Laura Falivene, Luigi Cavallo, Antoni A. Llobet, Montserrat Carmen Ríos Rodríguez, Isabel Romero, Miquel Solà

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

6 Scopus citations

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. © 2013 Elsevier B.V. All rights reserved.

Original language	English (US)
Pages (from-to)	142-146
Number of pages	5
Journal	Chemical Physics Letters
Volume	577
DOIs	https://doi.org/10.1016/j.cplett.2013.05.032
State	Published - Jul 2013

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: 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). Johnson & Matthey LTD are acknowledged for a RuCl3center dot nH2O loan. We also thank Centre de Supercomputacio de Catalunya (CESCA) for partial funding of computer time. The authors are extremely thankful for the helpful comments and assistance of Dr. Francesco Ragone.

ASJC Scopus subject areas

Physics and Astronomy(all)
Physical and Theoretical Chemistry

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10.1016/j.cplett.2013.05.032

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@article{656b2395b8004bdf9dcdef84ab769875,

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

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. {\textcopyright} 2013 Elsevier B.V. All rights reserved.",

author = "Albert Poater and Laura Falivene and Luigi Cavallo and Llobet, {Antoni A.} and Rodr{\'i}guez, {Montserrat Carmen R{\'i}os} and Isabel Romero and Miquel Sol{\`a}",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: 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). Johnson & Matthey LTD are acknowledged for a RuCl3center dot nH2O loan. We also thank Centre de Supercomputacio de Catalunya (CESCA) for partial funding of computer time. The authors are extremely thankful for the helpful comments and assistance of Dr. Francesco Ragone.",

year = "2013",

month = jul,

doi = "10.1016/j.cplett.2013.05.032",

language = "English (US)",

volume = "577",

pages = "142--146",

journal = "Chemical Physics Letters",

issn = "0009-2614",

publisher = "Elsevier",

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T1 - Simple and cheap steric and electronic characterization of the reactivity of Ru(II) complexes containing oxazoline ligands as epoxidation catalysts

AU - Poater, Albert

AU - Falivene, Laura

AU - Cavallo, Luigi

AU - Llobet, Antoni A.

AU - Rodríguez, Montserrat Carmen Ríos

AU - Romero, Isabel

AU - Solà, Miquel

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: 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). Johnson & Matthey LTD are acknowledged for a RuCl3center dot nH2O loan. We also thank Centre de Supercomputacio de Catalunya (CESCA) for partial funding of computer time. The authors are extremely thankful for the helpful comments and assistance of Dr. Francesco Ragone.

PY - 2013/7

Y1 - 2013/7

N2 - 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. © 2013 Elsevier B.V. All rights reserved.

AB - 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. © 2013 Elsevier B.V. All rights reserved.

UR - http://hdl.handle.net/10754/562839

UR - https://linkinghub.elsevier.com/retrieve/pii/S0009261413006623

UR - http://www.scopus.com/inward/record.url?scp=84879691945&partnerID=8YFLogxK

U2 - 10.1016/j.cplett.2013.05.032

DO - 10.1016/j.cplett.2013.05.032

M3 - Article

SN - 0009-2614

VL - 577

SP - 142

EP - 146

JO - Chemical Physics Letters

JF - Chemical Physics Letters

ER -

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

Abstract

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