(Catecholato)iron(III) complexes with tetradentate tripodal ligands containing substituted phenol and pyridine units as structural and functional model complexes for the catechol-bound intermediate of intradiol-cleaving catechol dioxygenases

Ryo Yamahara, Seiji Ogo, Yoshihito Watanabe, Takuzo Funabiki, Koichiro Jitsukawa, Hideki Masuda, Hisahiko Einaga

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Abstract

This paper reports the synthesis and structures of (catecholato)iron(III) complexes with tetradentate tripodal ligands (L(R',R'') = (2-hydroxy-3-R'-5-R''-phenyl-bis(2-pyridylmethyl)amine)) containing substituted phenol and pyridine units: [Fe(III)(L(R',R''))(DBC)] (1a: R',R'' = H,H; 1b: R',R'' = Me,Me; and 1c: R',R'' = H,Cl, DBC = 3,5-di-tert-butylcatecholato). X-ray structure analysis has revealed that the coordination arrangement around the iron atom of 1a is similar to that proposed for the active site of the catechol-bound intermediate of protocatechuate 3,4-dioxygenase (3,4-PCD). The series of complex 1 derivatives has been synthesized by two different methods: (i) reaction of [Fe(III)(L(R',R''))(acac)] + (2a: R',R''= H,H; 2b: R',R''= Me,Me; and 2c: R',R'' = H,Cl, acac = acetylacetonato) with 1 equiv. of DBC and 1 equiv. of Et 3 N in N,N-dimethylformamide (abbreviated as DMF), and (ii) reaction of [Fe(III)L(R',R''))Cl 2 ] (3a: R',R'' = H,H; 3b: R',R'' = Me,Me; and 3c: R',R'' = H,Cl) with 2 equiv. of AgOTf (OTf = O 3 SCF 3 - ), 1 equiv. of the catechols, and 2 equiv. of Et 3 N in DMF. The exogenous acac ligand of 2 acts as a Lewis base like the Tyr447 ligand in the active site of 3,4-PCD in the formation of the catechol-bound intermediate. Complexes 1, 2, and 3 have been characterized by X-ray analysis, visible and EPR spectroscopies, and cyclic voltammetry. Oxygenation of the bound DBC on 1 in the presence of O 2 has also been investigated and is discussed based on the Lewis basicity of the tripodal ligand containing the substituted phenolato group which is introduced to mimic the Tyr408 ligand of 3,4-PCD. (C) 2000 Elsevier Science S.A.

Original languageEnglish
Pages (from-to)587-596
Number of pages10
JournalInorganica Chimica Acta
Volume300-302
DOIs
Publication statusPublished - Apr 30 2000
Externally publishedYes

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Dioxygenases
Phenol
Pyridine
phenols
Phenols
pyridines
Iron
Ligands
iron
ligands
Protocatechuate-3,4-Dioxygenase
Lewis Bases
Catechols
Dimethylformamide
Lewis base
Oxygenation
oxygenation
X ray analysis
Alkalinity
Cyclic voltammetry

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

(Catecholato)iron(III) complexes with tetradentate tripodal ligands containing substituted phenol and pyridine units as structural and functional model complexes for the catechol-bound intermediate of intradiol-cleaving catechol dioxygenases. / Yamahara, Ryo; Ogo, Seiji; Watanabe, Yoshihito; Funabiki, Takuzo; Jitsukawa, Koichiro; Masuda, Hideki; Einaga, Hisahiko.

In: Inorganica Chimica Acta, Vol. 300-302, 30.04.2000, p. 587-596.

Research output: Contribution to journalArticle

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abstract = "This paper reports the synthesis and structures of (catecholato)iron(III) complexes with tetradentate tripodal ligands (L(R',R'') = (2-hydroxy-3-R'-5-R''-phenyl-bis(2-pyridylmethyl)amine)) containing substituted phenol and pyridine units: [Fe(III)(L(R',R''))(DBC)] (1a: R',R'' = H,H; 1b: R',R'' = Me,Me; and 1c: R',R'' = H,Cl, DBC = 3,5-di-tert-butylcatecholato). X-ray structure analysis has revealed that the coordination arrangement around the iron atom of 1a is similar to that proposed for the active site of the catechol-bound intermediate of protocatechuate 3,4-dioxygenase (3,4-PCD). The series of complex 1 derivatives has been synthesized by two different methods: (i) reaction of [Fe(III)(L(R',R''))(acac)] + (2a: R',R''= H,H; 2b: R',R''= Me,Me; and 2c: R',R'' = H,Cl, acac = acetylacetonato) with 1 equiv. of DBC and 1 equiv. of Et 3 N in N,N-dimethylformamide (abbreviated as DMF), and (ii) reaction of [Fe(III)L(R',R''))Cl 2 ] (3a: R',R'' = H,H; 3b: R',R'' = Me,Me; and 3c: R',R'' = H,Cl) with 2 equiv. of AgOTf (OTf = O 3 SCF 3 - ), 1 equiv. of the catechols, and 2 equiv. of Et 3 N in DMF. The exogenous acac ligand of 2 acts as a Lewis base like the Tyr447 ligand in the active site of 3,4-PCD in the formation of the catechol-bound intermediate. Complexes 1, 2, and 3 have been characterized by X-ray analysis, visible and EPR spectroscopies, and cyclic voltammetry. Oxygenation of the bound DBC on 1 in the presence of O 2 has also been investigated and is discussed based on the Lewis basicity of the tripodal ligand containing the substituted phenolato group which is introduced to mimic the Tyr408 ligand of 3,4-PCD. (C) 2000 Elsevier Science S.A.",
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T1 - (Catecholato)iron(III) complexes with tetradentate tripodal ligands containing substituted phenol and pyridine units as structural and functional model complexes for the catechol-bound intermediate of intradiol-cleaving catechol dioxygenases

AU - Yamahara, Ryo

AU - Ogo, Seiji

AU - Watanabe, Yoshihito

AU - Funabiki, Takuzo

AU - Jitsukawa, Koichiro

AU - Masuda, Hideki

AU - Einaga, Hisahiko

PY - 2000/4/30

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N2 - This paper reports the synthesis and structures of (catecholato)iron(III) complexes with tetradentate tripodal ligands (L(R',R'') = (2-hydroxy-3-R'-5-R''-phenyl-bis(2-pyridylmethyl)amine)) containing substituted phenol and pyridine units: [Fe(III)(L(R',R''))(DBC)] (1a: R',R'' = H,H; 1b: R',R'' = Me,Me; and 1c: R',R'' = H,Cl, DBC = 3,5-di-tert-butylcatecholato). X-ray structure analysis has revealed that the coordination arrangement around the iron atom of 1a is similar to that proposed for the active site of the catechol-bound intermediate of protocatechuate 3,4-dioxygenase (3,4-PCD). The series of complex 1 derivatives has been synthesized by two different methods: (i) reaction of [Fe(III)(L(R',R''))(acac)] + (2a: R',R''= H,H; 2b: R',R''= Me,Me; and 2c: R',R'' = H,Cl, acac = acetylacetonato) with 1 equiv. of DBC and 1 equiv. of Et 3 N in N,N-dimethylformamide (abbreviated as DMF), and (ii) reaction of [Fe(III)L(R',R''))Cl 2 ] (3a: R',R'' = H,H; 3b: R',R'' = Me,Me; and 3c: R',R'' = H,Cl) with 2 equiv. of AgOTf (OTf = O 3 SCF 3 - ), 1 equiv. of the catechols, and 2 equiv. of Et 3 N in DMF. The exogenous acac ligand of 2 acts as a Lewis base like the Tyr447 ligand in the active site of 3,4-PCD in the formation of the catechol-bound intermediate. Complexes 1, 2, and 3 have been characterized by X-ray analysis, visible and EPR spectroscopies, and cyclic voltammetry. Oxygenation of the bound DBC on 1 in the presence of O 2 has also been investigated and is discussed based on the Lewis basicity of the tripodal ligand containing the substituted phenolato group which is introduced to mimic the Tyr408 ligand of 3,4-PCD. (C) 2000 Elsevier Science S.A.

AB - This paper reports the synthesis and structures of (catecholato)iron(III) complexes with tetradentate tripodal ligands (L(R',R'') = (2-hydroxy-3-R'-5-R''-phenyl-bis(2-pyridylmethyl)amine)) containing substituted phenol and pyridine units: [Fe(III)(L(R',R''))(DBC)] (1a: R',R'' = H,H; 1b: R',R'' = Me,Me; and 1c: R',R'' = H,Cl, DBC = 3,5-di-tert-butylcatecholato). X-ray structure analysis has revealed that the coordination arrangement around the iron atom of 1a is similar to that proposed for the active site of the catechol-bound intermediate of protocatechuate 3,4-dioxygenase (3,4-PCD). The series of complex 1 derivatives has been synthesized by two different methods: (i) reaction of [Fe(III)(L(R',R''))(acac)] + (2a: R',R''= H,H; 2b: R',R''= Me,Me; and 2c: R',R'' = H,Cl, acac = acetylacetonato) with 1 equiv. of DBC and 1 equiv. of Et 3 N in N,N-dimethylformamide (abbreviated as DMF), and (ii) reaction of [Fe(III)L(R',R''))Cl 2 ] (3a: R',R'' = H,H; 3b: R',R'' = Me,Me; and 3c: R',R'' = H,Cl) with 2 equiv. of AgOTf (OTf = O 3 SCF 3 - ), 1 equiv. of the catechols, and 2 equiv. of Et 3 N in DMF. The exogenous acac ligand of 2 acts as a Lewis base like the Tyr447 ligand in the active site of 3,4-PCD in the formation of the catechol-bound intermediate. Complexes 1, 2, and 3 have been characterized by X-ray analysis, visible and EPR spectroscopies, and cyclic voltammetry. Oxygenation of the bound DBC on 1 in the presence of O 2 has also been investigated and is discussed based on the Lewis basicity of the tripodal ligand containing the substituted phenolato group which is introduced to mimic the Tyr408 ligand of 3,4-PCD. (C) 2000 Elsevier Science S.A.

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