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001-es BibID:BIBFORM079611
035-os BibID:(WoS)000412639800022 (Scopus)85030979850
Első szerző:Matyuska Ferenc
Cím:Control of structure, stability and catechol oxidase activity of copper(II) complexes by the denticity of tripodal platforms / Ferenc Matyuska, Nóra V. May, Attila Bényei, Tamás Gajda
Dátum:2017
ISSN:1144-0546 1369-9261
Megjegyzések:Copper(II) complexes of a new polydentate tripodal ligand trenpyz (L, tris[2-(5-pyrazolylmethyl)aminoethyl]- amine) were characterized in both solution and solid states. A combined evaluation of potentiometric UV-Vis and EPR data provided both thermodynamic and structural information on the complexes formed in solution. In equimolar solution the highly stable square pyramidal CuHL and trigonal bipyramidal CuL are the dominant species at around pH 3 and 5?8, respectively. Above pH 8 further deprotonation was observed (pK = 9.56), which is related to the formation of a copper(II)-bound pyrazolate anion. This creates the possibility for the formation of oligonuclear complexes, through pyrazolate bridges, and at a 3/2 Cu(II)/L ratio three trinuclear complexes were identified, similar to the copper(II)-tachpyz (N,N0 ,N00-tris(5-pyrazolylmethyl)-1,3,5-cis,cis-triamino-cyclohexane) system studied earlier. The trinuclear complexes of the two ligands have considerably different speciations, due to the different denticities of tripodal platforms. At the optimal pH the catechol oxidase activities of the triply deprotonated trinuclear complexes of trenpyz and tachpyz are similar, but the pH-rate constant profiles are significantly different, as a consequence of the deviations in their speciation. Consequently, the H2dtbc oxidation promoted by these trinuclear complexes can be easily controlled by the denticity of the tripodal ligands, since it affects the coordination environment of the central metal ion, which is proposed to be the main actor during the reaction.
Tárgyszavak:Természettudományok Kémiai tudományok idegen nyelvű folyóiratközlemény külföldi lapban
folyóiratcikk
Megjelenés:New Journal Of Chemistry. - 41 : 20 (2017), p. 11647-11660. -
További szerzők:May Nóra Veronika Bényei Attila (1962-) (vegyész) Gajda Tamás
Pályázati támogatás:GINOP-2.3.2-15-2016-00038
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OTKA 101541
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OTKA 115762
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001-es BibID:BIBFORM069193
035-os BibID:(WOS)000385198400018 (Scopus)84990944688
Első szerző:Szorcsik Attila
Cím:A novel 1,3,5-triaminocyclohexane-based tripodal ligand forms a unique tetra(pyrazolate)-bridged tricopper(II) core: solution equilibrium, structure and catecholase activity / Szorcsik Attila, Matyuska Ferenc, Bényei Attila, Nagy Nóra V., Szilágyi Róbert K., Gajda, Tamás
Dátum:2016
ISSN:1477-9226
Megjegyzések:Copper(II) complexes of a polydentate tripodal ligand L-3HCl (L = N,N',N"-tris(5-pyrazolylmethyl)-cis,cis-1,3,5-triaminocyclohexane) were characterized in both solution and solid states. Combined evaluation of potentiometric, UV-VIS, and EPR data indicated the formation of two mononuclear (CuHL, CuL) and three trinuclear (Cu3H-xL2, x = 2, 3, 4) complexes. The triply deprotonated trinuclear complex is an efficient catechol oxidase mimic with a surprisingly low pH optimum at pH = 5.6. Since the mononuclear CuL species is not able to promote the oxidation of 3,5-di-tert-butylcatechol, we assume that the central copper(II) ion of the trinuclear complex with unsaturated coordination sphere has fundamental role in the binding and oxidation of the substrate.The high stability and spectroscopic properties of the CuL species indicate the coordination of two pyrazole rings in addition to the three secondary amino groups of L in a square pyramidal geometry. Parallel with the formation of trinuclear species, intense charge transfer bands appear at around 400?500 nm, which indicate the formation of pyrazolate-bridged complexes. The crystal structure of [Cu3H-4L2](ClO4)2?5H2O (1) reveals the formation of a unique trinuclear complex that features a tetra(pyrazolate)-bridged linear tricopper(II) core. The Cu???Cu interatomic distances are around 3.8 ?A. The two peripheral copper(II) ions have slightly distorted square pyramidal geometry. The four pyrazole rings bound to the peripheral copper(II) ions are deprotonated that create a flattened tetrahedral environment for the central copper(II), i.e. the formation of the trinuclear complexes is under the allosteric control of the two peripheral copper(II) ions. The experimental structural details were further elaborated by a series of hybrid density functional theory calculations that support the presence of an antiferromagnetically coupled ground state. However, the magnitude and the pattern of spin coupling are dependent on the composition of the functionals. The optimized theoretical structures highlight the role of the crystal packing effects in inducing asymmetry between the two peripheral copper(II) sites.
Tárgyszavak:Természettudományok Kémiai tudományok idegen nyelvű folyóiratközlemény külföldi lapban
folyóiratcikk
Megjelenés:Dalton Transactions. - 45 : 38 (2016), p. 14998-15012. -
További szerzők:Matyuska Ferenc Bényei Attila (1962-) (vegyész) Nagy Nóra Veronika Szilágyi Róbert K. Gajda Tamás
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