TY - JOUR

T1 - Metal-mediated generation of triazapentadienate-terminated di- and trinuclear μ2-pyrazolate NiII species and control of their nuclearity

AU - Andrusenko, E.V.

AU - Kabin, E.V.

AU - Novikov, A.S.

AU - Bokach, N.A.

AU - Starova, G.L.

AU - Kukushkin, V.Yu.

N1 - cited By 4

PY - 2017

Y1 - 2017

N2 - © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.1,3,5-Triazapentadienate-terminated di- and trinuclear nickel(ii) complexes featuring bridging azolate ligands, [Ni2(μ2-azolate)2(TAP)2] (TAP = HN&cmb.b.line;&z.dbd;C(OMe)NC(OMe)&z.dbd;N&cmb.b.line;H; azole = 3,5-Me2pyrazole 2, 3,5-Ph2pyrazole 3) and [Ni3(μ2-azolate)4(TAP)2] (azole = 3,5-Me2pyrazole 4, indazole 5), were obtained from systems Ni2+/NCNR2/azole systems in MeOH. The terminal TAP ligands in the [Ni2(μ2-azolate)2(TAP)2] and [Ni3(μ2-azolate)4(TAP)2] species originate from the previously unreported cascade NiII-mediated and chelation-driven reaction between cyanamides and methanol. The oligomeric species and also [Ni(TAP)2] (1) are subject to interconversions that depend on the reactants involved and the reaction conditions. The control of the nuclearity of the complexes can be achieved by changing the amount of azoles or by their protonation, alteration of the steric hindrance of the substituents in the heterocycle

AB - © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.1,3,5-Triazapentadienate-terminated di- and trinuclear nickel(ii) complexes featuring bridging azolate ligands, [Ni2(μ2-azolate)2(TAP)2] (TAP = HN&cmb.b.line;&z.dbd;C(OMe)NC(OMe)&z.dbd;N&cmb.b.line;H; azole = 3,5-Me2pyrazole 2, 3,5-Ph2pyrazole 3) and [Ni3(μ2-azolate)4(TAP)2] (azole = 3,5-Me2pyrazole 4, indazole 5), were obtained from systems Ni2+/NCNR2/azole systems in MeOH. The terminal TAP ligands in the [Ni2(μ2-azolate)2(TAP)2] and [Ni3(μ2-azolate)4(TAP)2] species originate from the previously unreported cascade NiII-mediated and chelation-driven reaction between cyanamides and methanol. The oligomeric species and also [Ni(TAP)2] (1) are subject to interconversions that depend on the reactants involved and the reaction conditions. The control of the nuclearity of the complexes can be achieved by changing the amount of azoles or by their protonation, alteration of the steric hindrance of the substituents in the heterocycle

U2 - 10.1039/c6nj02962k

DO - 10.1039/c6nj02962k

M3 - Article

VL - 41

SP - 316

EP - 325

JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 1

ER -