The competition between acetate and pyrazolate in the formation of polynuclear Zn(II) coordination complexes
Articolo
Data di Pubblicazione:
2006
Citazione:
The competition between acetate and pyrazolate in the formation of polynuclear Zn(II) coordination complexes / A. Cingolani, S. Galli, N. Masciocchi, L. Pandolfo, C. Pettinari, A. Sironi. - In: DALTON TRANSACTIONS. - ISSN 1477-9226. - 20(2006), pp. 2479-2486. [10.1039/b515630k]
Abstract:
Hydrated zinc(II) acetate reacts with pyrazole (Hpz) and, depending on the reaction conditions, forms different pyrazole-containing species, i.e. [{Zn(CH3COO)(mu-pz)(Hpz)}(2)] (1), [{Zn(CH3COO)(2)(Hpz)(2)center dot CH3COOH}] (2), [{Zn(mu-pz)(2)}(n)] (3), and [{Zn(mu-CH3COO)(mu-pz)}(n)] (4). Their structural models have been derived from single-crystal X-ray diffractometry as well as from less conventional ab-initio X-ray powder methods. All species contain tetrahedrally coordinated Zn(II) ions, with Zn-N and Zn-O bond distances close to 2.0 angstrom. The existence of the {Zn(mu-pz)}(2) core in the species 1, 3 and 4 indicates the propensity for the formation, in the presence of pyrazolate ligands, of well-defined dinuclear entities (with Zn center dot center dot center dot Zn contacts in the range 3.6-3.8 angstrom). The latter can mutually interact, in the crystals, through either hydrogen-bonding of ancillary ligands (as in 1) or coordinative bonds (via acetates, as in 4, or by self-complementarity, as in 3). The interconversion paths among these species have been studied, employing chemical and thermal methods. In particular, the topotactic and quantitative transformation of 1 into 3 by moderate heating is likely based on a solid-state cooperative condensation mechanism of the dangling pyrazolates toward neighbouring zinc(II) ions, with concomitant acetic acid extrusion.
Tipologia IRIS:
01 - Articolo su periodico
Elenco autori:
A. Cingolani, S. Galli, N. Masciocchi, L. Pandolfo, C. Pettinari, A. Sironi
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