2001
DOI: 10.1039/b008511l
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The systematic influence of tripodal ligands on the catechol cleaving activity of iron(III) containing model compounds for catechol 1,2-dioxygenases †

Abstract: A series of mononuclear iron() complexes as functional and structural model compounds for intradiol cleaving catechol dioxygenases were synthesized. For all model compounds the iron() cores are in a distorted octahedral environment derived from tripodal tetradentate N 4 -donor ligands and a catechol. Model complexes for enzymesubstrate adducts were characterized by spectroscopic and electrochemical methods, and in four cases by singlecrystal X-ray crystallography. The systematic variation of one ligand a… Show more

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Cited by 101 publications
(132 citation statements)
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“…By adding non-oxidizable catechol such as tetrachlorocatechol (Cl 4 CatH 2 ) into the reaction mixture during the oxidation of 3,5-DTBCH 2 the reaction was stopped, supporting the inhibition effect of the Cl 4 CatH 2 , which can be explained by the catechol coordination [28,29]. As shown in Figure 6, in the series 3,5-DTBCH 2 , 4-t-butylcatechol (4-TBCatH 2 ), 4-methoxycatechol (4-MeOCatH 2 ), 4-methylcatechol (4-MeCatH 2 ) and catechol (CatH 2 ) the redox potentials increase due to the decreasing electron donating potential of the catechol substituents and the resulting decrease in Lewis basicity of the catechols [30]. With a higher electron donating character (lower redox potential) of the substrate, the charge donation from the coordinated catechol to the metal centers is increased in the dimetal-catechol intermediate, thereby making the substrate more prone to oxidation by O 2 [14].…”
Section: Oxidation Of 35-di-t-butylcatechol (Catecholase Activity)mentioning
confidence: 98%
“…By adding non-oxidizable catechol such as tetrachlorocatechol (Cl 4 CatH 2 ) into the reaction mixture during the oxidation of 3,5-DTBCH 2 the reaction was stopped, supporting the inhibition effect of the Cl 4 CatH 2 , which can be explained by the catechol coordination [28,29]. As shown in Figure 6, in the series 3,5-DTBCH 2 , 4-t-butylcatechol (4-TBCatH 2 ), 4-methoxycatechol (4-MeOCatH 2 ), 4-methylcatechol (4-MeCatH 2 ) and catechol (CatH 2 ) the redox potentials increase due to the decreasing electron donating potential of the catechol substituents and the resulting decrease in Lewis basicity of the catechols [30]. With a higher electron donating character (lower redox potential) of the substrate, the charge donation from the coordinated catechol to the metal centers is increased in the dimetal-catechol intermediate, thereby making the substrate more prone to oxidation by O 2 [14].…”
Section: Oxidation Of 35-di-t-butylcatechol (Catecholase Activity)mentioning
confidence: 98%
“…[4,46] Furthermore, several other systems with tripodal N 4 donor ligands showed considerable catechol dioxygenase activity. [47,48] Complexes with enzyme-analogous N 2 O 2 donor sets represent good structural and spectroscopic model compounds, however, they are poor functional models so far.…”
Section: Model Complexes For Intradiol Catechol Dioxygenasesmentioning
confidence: 99%
“…The starting complex [Ru(bbpaH)(dmso)Cl](PF 6 ) 2 was prepared by the reaction of Ru(dmso) 4 Cl 2 [25] and the bbpaH ligand [26] according to the literature procedure for the preparation of the analogous complex [Ru(tpa)(dmso)-Cl](PF 6 ) [tpa = tris(2-pyridylmethyl)amine]. [27] The subsequent reaction of [Ru(bbpaH)(dmso)Cl](PF 6 + were determined at -80°C by X-ray diffraction analyses.…”
Section: Resultsmentioning
confidence: 99%