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Issue 40, 2014
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NiII, CuII and ZnII complexes with a sterically hindered scorpionate ligand (TpmsPh) and catalytic application in the diasteroselective nitroaldol (Henry) reaction

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Abstract

The NiII and ZnII complexes [MCl(TpmsPh)] (TpmsPh = SO3C(pzPh)3, pz = pyrazolyl; M = Ni 2 or Zn 3) and the CuII complex [CuCl(TpmsPh)(H2O)] (4) have been prepared by treatment of the lithium salt of the sterically demanding and coordination flexible tris(3-phenyl-1-pyrazolyl)methanesulfonate (TpmsPh) (1) with the respective metal chlorides. The (TpmsPh) ligand shows the N3 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(TpmsPh)(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, 1H and 13C{1H} NMR, ESI-MS) data, density functional theory (DFT) methods and {for 4 and [nBu4N](TpmsPh) (7), the latter obtained upon Li+ replacement by [nBu4N]+ in Li(TpmsPh)} by single crystal X-ray diffraction analysis. The ZnII and CuII complexes (3 and 4, respectively) act as efficient catalyst precursors for the diastereoselective nitroaldol reaction of benzaldehydes and nitroethane to the corresponding β-nitroalkanols (up to 99% yield, at room temperature) with diastereoselectivity towards the formation of the anti isomer, whereas the NiII complex 2 only shows a modest catalytic activity.

Graphical abstract: NiII, CuII and ZnII complexes with a sterically hindered scorpionate ligand (TpmsPh) and catalytic application in the diasteroselective nitroaldol (Henry) reaction

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Publication details

The article was received on 22 May 2014, accepted on 15 Aug 2014 and first published on 15 Aug 2014


Article type: Paper
DOI: 10.1039/C4DT01509F
Author version available: Download Author version (PDF)
Citation: Dalton Trans., 2014,43, 15192-15200
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    NiII, CuII and ZnII complexes with a sterically hindered scorpionate ligand (TpmsPh) and catalytic application in the diasteroselective nitroaldol (Henry) reaction

    B. G. M. Rocha, T. C. O. Mac Leod, M. F. C. Guedes da Silva, K. V. Luzyanin, L. M. D. R. S. Martins and A. J. L. Pombeiro, Dalton Trans., 2014, 43, 15192
    DOI: 10.1039/C4DT01509F

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