Utilize este identificador para referenciar este registo: http://hdl.handle.net/10400.21/4955
Título: NiII, CuII and ZnII complexes with a sterically hindered scorpionate ligand (TpmsPh) and catalytic application in the diasteroselective nitroaldol (Henry) reaction
Autor: Rocha, Bruno G. M.
MacLeod, Tatiana C. O.
Silva, M. Fátima C. Guedes da
Luzyanin, Konstantin V.
Martins, Luísa Margarida D. R. S.
Pombeiro, Armando J. L.
Palavras-chave: Molecular-Orbital Methods
Valence Basis-Sets
Extended Basis-Sets
Gaussin-Type Basis
Cyclohexane Oxidation
Rhenium Complexes
Diastereoselective Synthesis
Organometallic Compounds
Peroxidative Oxidation
Data: 28-Out-2014
Editora: Royal Society of Chemistry
Citação: ROCHA, Bruno G. M.; [et al] – NiII, CuII and ZnII Complexes with a sterically hindered scorpionate ligand (TpmsPh) and catalytic application in the diasteroselective Nitroaldol (Henry) reaction. Dalton Transactions. ISSN: 1477-9226. Vol. 43, nr. 40 (2104), pp. 15192-15200
Resumo: The Ni-II and Zn-II complexes [MCl(Tpms(Ph))] (Tpms(Ph) = SO3C(pz(Ph))(3), pz = pyrazolyl; M = Ni 2 or Zn 3) and the Cu-II complex [CuCl(Tpms(Ph))(H2O)] (4) have been prepared by treatment of the lithium salt of the sterically demanding and coordination flexible tris(3-phenyl-1-pyrazolyl)methanesulfonate (Tpms(Ph))(-) (1) with the respective metal chlorides. The (Tpms(Ph))(-) ligand shows the N-3 or N2O coordination modes in 2 and 3 or in 4, respectively. Upon reaction of 2 and 3 with Ag(CF3SO3) in acetonitrile the complexes [M(Tpms(Ph))-(MeCN)](CF3SO3) (M = Ni 5 or Zn 6, respectively) were formed. The compounds were obtained in good yields and characterized by analytic and spectral (IR, H-1 and C-13{H-1} NMR, ESI-MS) data, density functional theory (DFT) methods and {for 4 and [(Bu4N)-Bu-n](Tpms(Ph)) (7), the tatter obtained upon Li+ replacement by [(Bu4N)-Bu-n](+) in Li(Tpms(Ph))} by single crystal X-ray diffraction analysis. The Zn-II and Cu-II complexes (3 and 4, respectively) act as efficient catalyst precursors for the diastereoselective nitroaldol reaction of benzaldehydes and nitroethane to the corresponding beta-nitroalkanols (up to 99% yield, at room temperature) with diastereoselectivity towards the formation of the anti isomer, whereas the Ni-II complex 2 only shows a modest catalytic activity.
Peer review: yes
URI: http://hdl.handle.net/10400.21/4955
DOI: 10.1039/c4dt01509f
ISSN: 1477-9226
Versão do Editor: http://pubs.rsc.org/en/content/articlepdf/2014/dt/c4dt01509f
Aparece nas colecções:ISEL - Eng. Quim. Biol. - Artigos

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