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Issue 30, 2017
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Metal-mediated reactions between dialkylcyanamides and acetamidoxime generate unusual (nitrosoguanidinate)nickel(II) complexes

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Abstract

The nitrosoguanidinate complexes [Ni{NH[double bond, length as m-dash]C(NR2)NN(O)}2] (R2 = Me21, (CH2)4O 2, (CH2)43, (CH2)54, (Me)Ph 5, Ph26, (p-MeC6H4)27) were obtained in low-to-moderate (12–26%) yields but reproducible yields in an unexpected metal-mediated reaction in MeOH between the nickel salt NiCl2·2H2O, N,N-disubstituted cyanamides NCNR2, and the amidoxime MeC([double bond, length as m-dash]NOH)NH2. These complexes were formed along with a spectrum of cyanamide–oxime coupling products. The IR and X-ray data indicate the delocalization within the NNO and NCN systems of the nitrosoguanidinate ligand. This delocalization was additionally confirmed by inspection of Wiberg bond indices for the selected bonds. In the X-ray structure of 5, the rare metallophilic contacts Ni⋯Ni between stacks of the square-planar complexes were detected and these non-covalent interactions were studied by non-relativistic and relativistic DFT calculations and topological analysis of the electron density distribution within the framework of Bader's theory (QTAIM method). The estimated strength of the Ni⋯Ni interactions is 1.3–1.9 kcal mol−1 and they are mostly determined by crystal packing effects and weak attractive interactions between adjacent metal centers due to the overlapping of their dz2 and pz orbitals.

Graphical abstract: Metal-mediated reactions between dialkylcyanamides and acetamidoxime generate unusual (nitrosoguanidinate)nickel(ii) complexes

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Publication details

The article was received on 31 May 2017, accepted on 09 Jul 2017 and first published on 10 Jul 2017


Article type: Paper
DOI: 10.1039/C7DT01960B
Citation: Dalton Trans., 2017,46, 10090-10101
  • Open access: Creative Commons BY-NC license
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    Metal-mediated reactions between dialkylcyanamides and acetamidoxime generate unusual (nitrosoguanidinate)nickel(II) complexes

    Z. M. Bikbaeva, A. S. Novikov, V. V. Suslonov, N. A. Bokach and V. Yu. Kukushkin, Dalton Trans., 2017, 46, 10090
    DOI: 10.1039/C7DT01960B

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