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Issue 10, 2014
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Halogen-bonded tris(2,4-bis(trichloromethyl)-1,3,5-triazapentadienato)-M(III) [M = Mn, Fe, Co] complexes and their catalytic activity in the peroxidative oxidation of 1-phenylethanol to acetophenone

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Abstract

One-pot template condensation of CCl3C[triple bond, length as m-dash]N with ammonia on a metal source [MnCl2·4H2O, FeCl3·6H2O or Co(CH3COO)2·4H2O] in DMSO led to the formation of tris{2,4-bis(trichloromethyl)-1,3,5-triazapentadienato}-M(III) complexes, [M{NH[double bond, length as m-dash]C(CCl3)NC(CCl3)[double bond, length as m-dash]NH}3n(CH3)2SO [M = Mn, n = 1 (1); M = Fe, n = 2 (2); M = Co, n = 2 (3)], which were characterized using elemental analysis, and IR, ESI-MS and single-crystal X-ray analysis. The role of inter- and intramolecular non-covalent halogen and hydrogen bonds in the synthesis of 1–3 is discussed. It is shown that the crystal ionic radii of the metal ions [68.5 (Co) < 69 (Fe) < 72 (Mn), pm] are related to the corresponding Cl⋯Cl distances [3.178 (3) > 3.155 (2) > 3.133 (1) Å]. Compounds 1–3 and the related di(triazapentadienato)-Cu(II) complex [Cu{NH[double bond, length as m-dash]C(CCl3)NC(CCl3)[double bond, length as m-dash]NH}2]·2(CH3)2SO (4) act as catalyst precursors for the additive-free microwave (MW) assisted homogeneous oxidation of 1-phenylethanol with tert-butylhydroperoxide (TBHP), leading to the formation of acetophenone with yields up to 99% and TONs up to 5.0 × 103 after 1 h of low power (10 W) MW irradiation.

Graphical abstract: Halogen-bonded tris(2,4-bis(trichloromethyl)-1,3,5-triazapentadienato)-M(iii) [M = Mn, Fe, Co] complexes and their catalytic activity in the peroxidative oxidation of 1-phenylethanol to acetophenone

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Publication details

The article was received on 16 May 2014, accepted on 19 Jul 2014 and first published on 21 Jul 2014


Article type: Paper
DOI: 10.1039/C4NJ00797B
Citation: New J. Chem., 2014,38, 4807-4815
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    Halogen-bonded tris(2,4-bis(trichloromethyl)-1,3,5-triazapentadienato)-M(III) [M = Mn, Fe, Co] complexes and their catalytic activity in the peroxidative oxidation of 1-phenylethanol to acetophenone

    N. Q. Shixaliyev, A. V. Gurbanov, A. M. Maharramov, K. T. Mahmudov, M. N. Kopylovich, L. M. D. R. S. Martins, V. M. Muzalevskiy, V. G. Nenajdenko and A. J. L. Pombeiro, New J. Chem., 2014, 38, 4807
    DOI: 10.1039/C4NJ00797B

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