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New Ru (II) complexes containing oxazoline ligands as epoxidation catalysts: influence of the substituents on the catalytic performance

The synthesis of a family of new Ru complexes containing the facial tridentate ligand with general formula [RuII(T)(D)(X)]n+ (T = trispyrazolylmethane (tpm); D = ((4S,4′S)-(-)-4,4′,5,5′- tetrahydro-4,4′-bis(1-methylethyl)-2,2′-bioxazole) (iPr-box-C) or N-(1-hydroxy-3-methylbutan-(2S)-(-)-2-yl)-(4S)-(-)-4-isopropyl-4, 5-dihydrooxazole-2-carbimidate (iPr-box-O); X = Cl, H2O) has been described. All complexes have been spectroscopically characterized in solution through 1H NMR and UV-vis techniques, and the redox properties of complexes have also been studied by means of cyclic voltammetry (CV). Furthermore, the chloro complexes presented here have been characterized in the solid state through monocrystal X-ray diffraction analysis. The oxazolinic iPr-box-C ligand undergoes a Ru-assisted hydrolysis reaction generating the corresponding amidate anionic ligand iPr-box-O, that keeps coordinated to the Ru metal center and that produces a strong σ-donation effect over it. The reactivity of the Ru-OH2 complexes described in this paper together with other similar ones, previously synthesized by us, has been tested with regard to the epoxidation of different olefins. Complexes [Ru II(R-box-C)(tpm)OH2](BF4)2, R = Bz, 3′c/iPr, 3c, show high stereoselectivity in the epoxidation of cis-β-methylstyrene, with the exclusive formation of the cis-epoxide. However, there is a significant difference in regioselectivity between the two catalysts in the epoxidation of 4-vinylcyclohexene; complex 3′c leads to the regioselective oxidation at the ring alkene position, whereas complex 3c leads to the oxidation at the terminal position. Computational calculations indicate only small energy differences between the two possible products of 4-vinylcyclohexene epoxidation, but the energy barriers for the interaction of the catalytic systems with the alkene groups of 4-vinylcyclohexene agree with the reactivity differences found for the two catalysts having isopropyl or benzyl as substituent of the oxazole ligand. Computed local Fukui functions help to explain the observed reactivity trends

We acknowledge financial support from the MICINNof Spain (CTQ2010-21532-C02-01 to I.R. and M.R., CTQ2009-08328 to T.P., CTQ2010-21497 and Consolider Ingenio 2010 CSD2006-0003 to A.L. and CTQ2008-03077/BQU to M.S.) and the DIUE of Catalonia (2009SGR637). 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 Ram on y Cajal contract (ref RYC-2009-04170). Johnson & Matthey LTD are acknowledged for a RuCl3 3 nH2O loan. We also thank Centre de Supercomputaci o de Catalunya (CESCA) for partial funding of computer time

© Inorganic Chemistry, 2011, vol. 50, núm. 13, p. 6044-6054

American Chemical Society (ACS)

Manager: Ministerio de Ciencia e Innovación (Espanya)
Ministerio de Educación y Ciencia (Espanya)
Author: Serrano Núñez, Isabel
López, M. Isabel
Ferrer Vall-llosada, Íngrid
Poater Teixidor, Albert
Parella Coll, Teodor
Fontrodona, Xavier
Solà i Puig, Miquel
Llobet Dalmases, Antoni
Rodríguez Pizarro, Montserrat
Romero García, Isabel
Date: 2011 July 4
Abstract: The synthesis of a family of new Ru complexes containing the facial tridentate ligand with general formula [RuII(T)(D)(X)]n+ (T = trispyrazolylmethane (tpm); D = ((4S,4′S)-(-)-4,4′,5,5′- tetrahydro-4,4′-bis(1-methylethyl)-2,2′-bioxazole) (iPr-box-C) or N-(1-hydroxy-3-methylbutan-(2S)-(-)-2-yl)-(4S)-(-)-4-isopropyl-4, 5-dihydrooxazole-2-carbimidate (iPr-box-O); X = Cl, H2O) has been described. All complexes have been spectroscopically characterized in solution through 1H NMR and UV-vis techniques, and the redox properties of complexes have also been studied by means of cyclic voltammetry (CV). Furthermore, the chloro complexes presented here have been characterized in the solid state through monocrystal X-ray diffraction analysis. The oxazolinic iPr-box-C ligand undergoes a Ru-assisted hydrolysis reaction generating the corresponding amidate anionic ligand iPr-box-O, that keeps coordinated to the Ru metal center and that produces a strong σ-donation effect over it. The reactivity of the Ru-OH2 complexes described in this paper together with other similar ones, previously synthesized by us, has been tested with regard to the epoxidation of different olefins. Complexes [Ru II(R-box-C)(tpm)OH2](BF4)2, R = Bz, 3′c/iPr, 3c, show high stereoselectivity in the epoxidation of cis-β-methylstyrene, with the exclusive formation of the cis-epoxide. However, there is a significant difference in regioselectivity between the two catalysts in the epoxidation of 4-vinylcyclohexene; complex 3′c leads to the regioselective oxidation at the ring alkene position, whereas complex 3c leads to the oxidation at the terminal position. Computational calculations indicate only small energy differences between the two possible products of 4-vinylcyclohexene epoxidation, but the energy barriers for the interaction of the catalytic systems with the alkene groups of 4-vinylcyclohexene agree with the reactivity differences found for the two catalysts having isopropyl or benzyl as substituent of the oxazole ligand. Computed local Fukui functions help to explain the observed reactivity trends
We acknowledge financial support from the MICINNof Spain (CTQ2010-21532-C02-01 to I.R. and M.R., CTQ2009-08328 to T.P., CTQ2010-21497 and Consolider Ingenio 2010 CSD2006-0003 to A.L. and CTQ2008-03077/BQU to M.S.) and the DIUE of Catalonia (2009SGR637). 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 Ram on y Cajal contract (ref RYC-2009-04170). Johnson & Matthey LTD are acknowledged for a RuCl3 3 nH2O loan. We also thank Centre de Supercomputaci o de Catalunya (CESCA) for partial funding of computer time
Format: application/pdf
Citation: 015414
ISSN: 0020-1669 (versió paper)
1520-510X (versió electrònica)
Document access: http://hdl.handle.net/10256/11724
Language: eng
Publisher: American Chemical Society (ACS)
Collection: MICINN/PN 2011-2014/CTQ2010-21532-C02-01
MEC/PN 2009-2011/CTQ2008-03077/BQU
Reproducció digital del document publicat a: http://dx.doi.org/10.1021/ic200053f
Articles publicats (D-Q)
Is part of: © Inorganic Chemistry, 2011, vol. 50, núm. 13, p. 6044-6054
Rights: Tots els drets reservats
Subject: Ruteni -- Compostos
Ruthenium compounds
Catàlisi
Catalysis
Epòxids
Epoxy compounds
Title: New Ru (II) complexes containing oxazoline ligands as epoxidation catalysts: influence of the substituents on the catalytic performance
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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