Synthesis and structure study of some catecholase-mimetic iron complexes

T. Megyes, Zoltán May, G. Schubert, T. Grósz, László I. Simándi, T. Radnái

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

The biomimetic dioximatoiron complexes [Fe(Hdmed)]+ and [Fe(H2dmdt)]2+ act as catecholase models but the latter also catalyzes the intradiol cleavage of 3,5-ditert-butylcatechol. This remarkable selectivity was ascribed to the stable, hydrogen-bonded, macrocyclic coordination sphere of [Fe(Hdmed)]+, precluding bidentate catechol binding, as opposed to the less stable, mobile structure of [Fe(H2dmdt)]2+. This hypothesis is supported by the structures of [Fe(Hdmed)]+ and [Fe(H2dmdt)]2+ determined by X-ray diffraction in 1 M methanol solution. This study is a demonstrative example for the capabilities of the X-ray diffraction technique applied for complexes in the solution phase. The characteristic bond lengths of the complex and the number of solvent molecules in the solvation shell have been determined. To examine the structure of the complexes, gas phase density functional geometry optimizations were performed by using the adf-2004.01 and gaussian-98 packages. The PCM methodology was applied to estimate the effect of solvent on the relative energetics of the low-spin and high-spin electronic states of the complexes. The calculations confirmed that the electronic ground state corresponds to the triplet state for both complexes.

Original languageEnglish
Pages (from-to)2329-2336
Number of pages8
JournalInorganica Chimica Acta
Volume359
Issue number8
DOIs
Publication statusPublished - May 15 2006

Fingerprint

X-Ray Diffraction
Iron
complex numbers
iron
X ray diffraction
Biomimetics
Pulse code modulation
biomimetics
Solvation
Bond length
Electronic states
synthesis
electronics
diffraction
Ground state
atomic energy levels
solvation
Methanol
cleavage
Hydrogen

Keywords

  • Cathecolase mimetic action
  • Iron(II) complexes
  • Solution structure
  • Structure of complexes
  • X-ray diffraction

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Synthesis and structure study of some catecholase-mimetic iron complexes. / Megyes, T.; May, Zoltán; Schubert, G.; Grósz, T.; Simándi, László I.; Radnái, T.

In: Inorganica Chimica Acta, Vol. 359, No. 8, 15.05.2006, p. 2329-2336.

Research output: Contribution to journalArticle

@article{8ebd375ce3794e5c85da5021d35a6033,
title = "Synthesis and structure study of some catecholase-mimetic iron complexes",
abstract = "The biomimetic dioximatoiron complexes [Fe(Hdmed)]+ and [Fe(H2dmdt)]2+ act as catecholase models but the latter also catalyzes the intradiol cleavage of 3,5-ditert-butylcatechol. This remarkable selectivity was ascribed to the stable, hydrogen-bonded, macrocyclic coordination sphere of [Fe(Hdmed)]+, precluding bidentate catechol binding, as opposed to the less stable, mobile structure of [Fe(H2dmdt)]2+. This hypothesis is supported by the structures of [Fe(Hdmed)]+ and [Fe(H2dmdt)]2+ determined by X-ray diffraction in 1 M methanol solution. This study is a demonstrative example for the capabilities of the X-ray diffraction technique applied for complexes in the solution phase. The characteristic bond lengths of the complex and the number of solvent molecules in the solvation shell have been determined. To examine the structure of the complexes, gas phase density functional geometry optimizations were performed by using the adf-2004.01 and gaussian-98 packages. The PCM methodology was applied to estimate the effect of solvent on the relative energetics of the low-spin and high-spin electronic states of the complexes. The calculations confirmed that the electronic ground state corresponds to the triplet state for both complexes.",
keywords = "Cathecolase mimetic action, Iron(II) complexes, Solution structure, Structure of complexes, X-ray diffraction",
author = "T. Megyes and Zolt{\'a}n May and G. Schubert and T. Gr{\'o}sz and Sim{\'a}ndi, {L{\'a}szl{\'o} I.} and T. Radn{\'a}i",
year = "2006",
month = "5",
day = "15",
doi = "10.1016/j.ica.2005.05.041",
language = "English",
volume = "359",
pages = "2329--2336",
journal = "Inorganica Chimica Acta",
issn = "0020-1693",
publisher = "Elsevier BV",
number = "8",

}

TY - JOUR

T1 - Synthesis and structure study of some catecholase-mimetic iron complexes

AU - Megyes, T.

AU - May, Zoltán

AU - Schubert, G.

AU - Grósz, T.

AU - Simándi, László I.

AU - Radnái, T.

PY - 2006/5/15

Y1 - 2006/5/15

N2 - The biomimetic dioximatoiron complexes [Fe(Hdmed)]+ and [Fe(H2dmdt)]2+ act as catecholase models but the latter also catalyzes the intradiol cleavage of 3,5-ditert-butylcatechol. This remarkable selectivity was ascribed to the stable, hydrogen-bonded, macrocyclic coordination sphere of [Fe(Hdmed)]+, precluding bidentate catechol binding, as opposed to the less stable, mobile structure of [Fe(H2dmdt)]2+. This hypothesis is supported by the structures of [Fe(Hdmed)]+ and [Fe(H2dmdt)]2+ determined by X-ray diffraction in 1 M methanol solution. This study is a demonstrative example for the capabilities of the X-ray diffraction technique applied for complexes in the solution phase. The characteristic bond lengths of the complex and the number of solvent molecules in the solvation shell have been determined. To examine the structure of the complexes, gas phase density functional geometry optimizations were performed by using the adf-2004.01 and gaussian-98 packages. The PCM methodology was applied to estimate the effect of solvent on the relative energetics of the low-spin and high-spin electronic states of the complexes. The calculations confirmed that the electronic ground state corresponds to the triplet state for both complexes.

AB - The biomimetic dioximatoiron complexes [Fe(Hdmed)]+ and [Fe(H2dmdt)]2+ act as catecholase models but the latter also catalyzes the intradiol cleavage of 3,5-ditert-butylcatechol. This remarkable selectivity was ascribed to the stable, hydrogen-bonded, macrocyclic coordination sphere of [Fe(Hdmed)]+, precluding bidentate catechol binding, as opposed to the less stable, mobile structure of [Fe(H2dmdt)]2+. This hypothesis is supported by the structures of [Fe(Hdmed)]+ and [Fe(H2dmdt)]2+ determined by X-ray diffraction in 1 M methanol solution. This study is a demonstrative example for the capabilities of the X-ray diffraction technique applied for complexes in the solution phase. The characteristic bond lengths of the complex and the number of solvent molecules in the solvation shell have been determined. To examine the structure of the complexes, gas phase density functional geometry optimizations were performed by using the adf-2004.01 and gaussian-98 packages. The PCM methodology was applied to estimate the effect of solvent on the relative energetics of the low-spin and high-spin electronic states of the complexes. The calculations confirmed that the electronic ground state corresponds to the triplet state for both complexes.

KW - Cathecolase mimetic action

KW - Iron(II) complexes

KW - Solution structure

KW - Structure of complexes

KW - X-ray diffraction

UR - http://www.scopus.com/inward/record.url?scp=84962374499&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84962374499&partnerID=8YFLogxK

U2 - 10.1016/j.ica.2005.05.041

DO - 10.1016/j.ica.2005.05.041

M3 - Article

AN - SCOPUS:84962374499

VL - 359

SP - 2329

EP - 2336

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

SN - 0020-1693

IS - 8

ER -