Synthesis and characterization of inner-sphere substitution products in azide-containing сobalt(III) dioximates
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COROPCEANU, Eduard, BOLOGA, Olga, ARSENE, Ion, VITIU (BOLDIŞOR), Aliona, BULHAK, Ion, GORINCHOY, Natalia, BOUROSH, Pavlina. Synthesis and characterization of inner-sphere substitution products in azide-containing сobalt(III) dioximates. In: Russian Journal of Coordination Chemistry/Koordinatsionnaya Khimiya, 2016, vol. 42, pp. 516-538. ISSN -. DOI: https://doi.org/10.1134/S1070328416070046
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Russian Journal of Coordination Chemistry/Koordinatsionnaya Khimiya
Volumul 42 / 2016 / ISSN - /ISSNe 1070-3284

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

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

Pag. 516-538

Coropceanu Eduard1, Bologa Olga1, Arsene Ion1, Vitiu (Boldişor) Aliona2, Bulhak Ion1, Gorinchoy Natalia1, Bourosh Pavlina2
 
1 Institute of Chemistry of the Academy of Sciences of Moldova,
2 Institute of Applied Physics, Academy of Sciences of Moldova
 
 
Disponibil în IBN: 27 februarie 2020


Rezumat

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)22О)] 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)22О)] 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 N3 -. 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 N3 - anion on the bond lengths along the axial coordinate and on the Со–N bonds in the equatorial plane of the octahedron. 

Cuvinte-cheie
Amides, Bond length, Ions, ligands, Molecules, Nuclear magnetic resonance spectroscopy, Pyridine, Substitution reactions, Sulfur dioxide, Synthesis (chemical), X ray diffraction analysis