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Synthesis and characterization of inner-sphere substitution products in azide-containing сobalt(III) dioximates

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Abstract

New compounds of Co(III) dimethylglyoximate with the sulfanilamide derivative [Co(N3)(DmgH)2(SAM)] (DmgH– is the dimethylglyoxime monoanion, and SAM is–NH2–C6H4–SO2–NH–R) are synthesized using the structural block [Co(N3)(DmgH)2(Н2О)] as the initial one. The reaction products of various [Co(N3)(DmgH)2(SAM)] with ligand L (L is pyridine (Py), thiourea (Thio), triphenylphosphine (PPh3), nicotinamide (Nia), iso-nicotinamide (INia), isonicotinic acid (НINА), 4-pyridinaldoxime (4-PaoH), 4,4’-bipyridine (Bipy), and NH4NCS) are synthesized. The compounds are studied by IR and NMR spectroscopy and X-ray diffraction analysis (CIF files CCDC 1414767–1414775 (I, V–XII)). The following facts are established. First, only the coordinated water molecule in [Co(N3)(DmgH)2(Н2О)] is replaced by SAM. Second, SAM from different similar compounds also undergoes substitution by the aforementioned organic ligands. The exception is the compound obtained by the reaction of [Co(N3)(DmgH)2(SAM)] with NH4NCS, due to which the NCS– anion replaces both SAM and inorganic anion N -3 . The X-ray diffraction analysis shows that the substitution reactions give both mononuclear compounds [Со(N3)(DmgH)2(Py)], [Со(N3)(DmgH)2(PPh3)], [Со(N3)(DmgH)2(Thio)], [Со(N3)(DmgH)2(Nia)] [Со(N3)(DmgH)2(INia)], [Со(N3)(DmgH)2(HINА)] ∙ H2O, [Со(N3)(DmgH)2(4-PaoH)] ∙ DMF, and [Со(N3)(DmgH)2(Bipy)] and binuclear molecular complexes [(Со(N3)(DmgH)2)2(Bipy)] ∙ 0.5H2O and [(Со(N3)(DmgH)2)2(Bipy)] ∙ H2O, as well as ionic complex (NH4)[Co(SCN)2(DmgH)2] ∙ 3H2O. The obtained compounds supplement a series of complexes that make it possible to evaluate the trans effect of the N -3 anion on the bond lengths along the axial coordinate and on the Со–N bonds in the equatorial plane of the octahedron.

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Authors and Affiliations

  1. Institute of Chemistry, Academy of Sciences of Moldova, Chisinau, Republic of Moldova

    E. Coropceanu, O. Bologa, I. Arsene, I. Bulhac & N. Gorinchioy

  2. Institute of Applied Physics, Academy of Sciences of Moldova, Chisinau, Republic of Moldova

    A. Vitiu & P. Bourosh

Authors
  1. E. Coropceanu
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  2. O. Bologa
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  3. I. Arsene
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  4. A. Vitiu
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  5. I. Bulhac
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  6. N. Gorinchioy
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  7. P. Bourosh
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Correspondence to P. Bourosh.

Additional information

Dedicated to the 110th anniversary of the discovery of the reaction of transition metals with α-dioximes by Academician L.A. Chugaev and to the 110th birthday of Academician A.V. Ablov, the founder of the school of coordination chemistry in Chisinau

Original Russian Text © E. Coropceanu, O. Bologa, I. Arsene, A. Vitiu, I. Bulhac, N. Gorinchioy, P. Bourosh, 2016, published in Koordinatsionnaya Khimiya, 2016, Vol. 42, No. 8, pp. 480–502.

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Coropceanu, E., Bologa, O., Arsene, I. et al. Synthesis and characterization of inner-sphere substitution products in azide-containing сobalt(III) dioximates. Russ J Coord Chem 42, 516–538 (2016). https://doi.org/10.1134/S1070328416070046

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  • DOI: https://doi.org/10.1134/S1070328416070046

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