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Zinc(II) Complexes with Asymmetric 3,5-Substituted 1H-Pyrazoles

Malinkin, Sergey O.; Penkova, Larysa; Moroz, Yurii S.; Haukka, Matti; Maciag, Anna; Gumienna-Kontecka, Elzbieta; Pavlenko, Vadim A.; Pavlova, Svetlana; Nordlander, Ebbe LU and Fritsky, Igor O. (2012) In European Journal of Inorganic Chemistry p.1639-1649
Abstract
Two new pyrazolate-based ligands, N'-[1-(3-acetyl-4-methyl-1H-pyrazol-5-yl)ethylidene]-2-(hydroxyimino)propanehydrazide (L1) and 5-[(E)-1-(2-{(E)-2-(hydroxyimino}propanoyl}hydrazono)ethyl]-4-methyl-1H-pyrazole-3-carboxylic acid (L2), were synthesized and studied for zinc(II) complexation. A set of pH-dependent UV/Vis measurements has been performed to determine the complex formation properties of L2. According to the calculations, in solution, L2 forms variously protonated mononuclear (ZnII/L2 = 1:1) and dinuclear (ZnII/L2 = 2:1) complexes. The reaction of the deprotonated ligands with hydrated ZnII salts and slow diffusion of ammonia into the reaction mixtures gave mononuclear [Zn(L1-2H)(NH3)2]center dot DMF (1) and trinuclear... (More)
Two new pyrazolate-based ligands, N'-[1-(3-acetyl-4-methyl-1H-pyrazol-5-yl)ethylidene]-2-(hydroxyimino)propanehydrazide (L1) and 5-[(E)-1-(2-{(E)-2-(hydroxyimino}propanoyl}hydrazono)ethyl]-4-methyl-1H-pyrazole-3-carboxylic acid (L2), were synthesized and studied for zinc(II) complexation. A set of pH-dependent UV/Vis measurements has been performed to determine the complex formation properties of L2. According to the calculations, in solution, L2 forms variously protonated mononuclear (ZnII/L2 = 1:1) and dinuclear (ZnII/L2 = 2:1) complexes. The reaction of the deprotonated ligands with hydrated ZnII salts and slow diffusion of ammonia into the reaction mixtures gave mononuclear [Zn(L1-2H)(NH3)2]center dot DMF (1) and trinuclear mu-pyrazolato-bridged [Zn3(L2-3H)2(NH3)5]center dot 4H2O (3). In both complexes, the zinc ions are in the same distorted trigonal-bipyramidal environment, coordinated to two nitrogen atoms of the ammonia and one oxygen and two nitrogen atoms of the pyrazolate and hydrazide groups. The molecular structures of all of the ligands and complexes have been elucidated by X-ray crystallography. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
N, O ligands, Zinc, Structure elucidation
in
European Journal of Inorganic Chemistry
issue
10
pages
1639 - 1649
publisher
John Wiley & Sons
external identifiers
  • wos:000301986600009
  • scopus:84859094557
ISSN
1099-0682
DOI
10.1002/ejic.201101090
language
English
LU publication?
yes
id
94e966de-5e12-4687-8fe5-41164538880d (old id 2574833)
date added to LUP
2012-06-04 12:48:52
date last changed
2017-01-01 03:31:15
@article{94e966de-5e12-4687-8fe5-41164538880d,
  abstract     = {Two new pyrazolate-based ligands, N'-[1-(3-acetyl-4-methyl-1H-pyrazol-5-yl)ethylidene]-2-(hydroxyimino)propanehydrazide (L1) and 5-[(E)-1-(2-{(E)-2-(hydroxyimino}propanoyl}hydrazono)ethyl]-4-methyl-1H-pyrazole-3-carboxylic acid (L2), were synthesized and studied for zinc(II) complexation. A set of pH-dependent UV/Vis measurements has been performed to determine the complex formation properties of L2. According to the calculations, in solution, L2 forms variously protonated mononuclear (ZnII/L2 = 1:1) and dinuclear (ZnII/L2 = 2:1) complexes. The reaction of the deprotonated ligands with hydrated ZnII salts and slow diffusion of ammonia into the reaction mixtures gave mononuclear [Zn(L1-2H)(NH3)2]center dot DMF (1) and trinuclear mu-pyrazolato-bridged [Zn3(L2-3H)2(NH3)5]center dot 4H2O (3). In both complexes, the zinc ions are in the same distorted trigonal-bipyramidal environment, coordinated to two nitrogen atoms of the ammonia and one oxygen and two nitrogen atoms of the pyrazolate and hydrazide groups. The molecular structures of all of the ligands and complexes have been elucidated by X-ray crystallography.},
  author       = {Malinkin, Sergey O. and Penkova, Larysa and Moroz, Yurii S. and Haukka, Matti and Maciag, Anna and Gumienna-Kontecka, Elzbieta and Pavlenko, Vadim A. and Pavlova, Svetlana and Nordlander, Ebbe and Fritsky, Igor O.},
  issn         = {1099-0682},
  keyword      = {N,O ligands,Zinc,Structure elucidation},
  language     = {eng},
  number       = {10},
  pages        = {1639--1649},
  publisher    = {John Wiley & Sons},
  series       = {European Journal of Inorganic Chemistry},
  title        = {Zinc(II) Complexes with Asymmetric 3,5-Substituted 1H-Pyrazoles},
  url          = {http://dx.doi.org/10.1002/ejic.201101090},
  year         = {2012},
}