A highly reactive functional model for the catechol dioxygenases. structure and properties of [Fe(TPA)DBC]BPh4

Ho Gyeom Jang, David D. Cox, Lawrence Que

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Abstract

[FeIII(TPA)DBC]BPh4, a new functional model for the catechol dioxygenases, has been synthesized, where is tris(2-pyridylmethyl)amine and DBC is 3,-di-tert-butylcatecholate dianion. The TPA with complex reacts with O2 within minutes to afford intradiol cleavage, in 98% yield, which is the highest convesion obsesrved of all [Fe(L)DBC] complexes studied. More interestingly, the TPA complex is the fastest reacting of all the [Fe(L)DBC] complexes studied. Kinetic studies of the reaction of the complex with 1 atm of O2 in DMF under pseudo-first-order- conditions show that the TPA complex react appproximately three orders of magnitude faster than the corresponding NTA complex, where NTA is N,N- bis(carboxymethyl)glycine. Both the high specificity and the fast kinetics can be associated with the high Lewis acidity of athe ferric center in the TPA complex. To investigate the factors determining reactivity, we have solved the crystal structure of [Fe(TPA)DBC]BPh4 (space group P1̄ a = 12.464 (5) ̊, b = 13.480 (6) ̊, c = 15.980 (8) ̊, α = 85.11 (4)°, β =83.96 (4)°, γ ?? 70.76 (4)° V = 2517 (4) ̊3, Z = 2, R = 0.054 and Rw = 0.063). Compared with other complexes in the [Fe(L)DBC] series, the iron-catecholate interaction in the TPA complex is significantly stronger, resulting in the enhanced covalency of the metal-catecholate bonds and low-energy catecholate LMCT bands. The enhanced covalency is reflected by the isotropic shifts exibited by the DBC protons, which indicate increased semiquinone character. The greater semiquinone character in the TPA complex correlates well its high reactivity toaward O2. These trends provide substantial evidence for the substrate activitation mechanism proposed for the oxidative cleavage of catechols.

Original languageEnglish
Pages (from-to)9200-9204
Number of pages5
JournalJournal of the American Chemical Society
Volume113
Issue number24
Publication statusPublished - 1991 Dec 1
Externally publishedYes

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Dioxygenases
Nitrilotriacetic Acid
Catechols
Kinetics
Acidity
Protons
Amino acids
Amines
Iron
Crystal structure
Metals
Substrates
catechol
tris(2-pyridylmethyl)amine

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

A highly reactive functional model for the catechol dioxygenases. structure and properties of [Fe(TPA)DBC]BPh4 . / Jang, Ho Gyeom; Cox, David D.; Que, Lawrence.

In: Journal of the American Chemical Society, Vol. 113, No. 24, 01.12.1991, p. 9200-9204.

Research output: Contribution to journalArticle

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title = "A highly reactive functional model for the catechol dioxygenases. structure and properties of [Fe(TPA)DBC]BPh4",
abstract = "[FeIII(TPA)DBC]BPh4, a new functional model for the catechol dioxygenases, has been synthesized, where is tris(2-pyridylmethyl)amine and DBC is 3,-di-tert-butylcatecholate dianion. The TPA with complex reacts with O2 within minutes to afford intradiol cleavage, in 98{\%} yield, which is the highest convesion obsesrved of all [Fe(L)DBC] complexes studied. More interestingly, the TPA complex is the fastest reacting of all the [Fe(L)DBC] complexes studied. Kinetic studies of the reaction of the complex with 1 atm of O2 in DMF under pseudo-first-order- conditions show that the TPA complex react appproximately three orders of magnitude faster than the corresponding NTA complex, where NTA is N,N- bis(carboxymethyl)glycine. Both the high specificity and the fast kinetics can be associated with the high Lewis acidity of athe ferric center in the TPA complex. To investigate the factors determining reactivity, we have solved the crystal structure of [Fe(TPA)DBC]BPh4 (space group P1̄ a = 12.464 (5) ̊, b = 13.480 (6) ̊, c = 15.980 (8) ̊, α = 85.11 (4)°, β =83.96 (4)°, γ ?? 70.76 (4)° V = 2517 (4) ̊3, Z = 2, R = 0.054 and Rw = 0.063). Compared with other complexes in the [Fe(L)DBC] series, the iron-catecholate interaction in the TPA complex is significantly stronger, resulting in the enhanced covalency of the metal-catecholate bonds and low-energy catecholate LMCT bands. The enhanced covalency is reflected by the isotropic shifts exibited by the DBC protons, which indicate increased semiquinone character. The greater semiquinone character in the TPA complex correlates well its high reactivity toaward O2. These trends provide substantial evidence for the substrate activitation mechanism proposed for the oxidative cleavage of catechols.",
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T1 - A highly reactive functional model for the catechol dioxygenases. structure and properties of [Fe(TPA)DBC]BPh4

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N2 - [FeIII(TPA)DBC]BPh4, a new functional model for the catechol dioxygenases, has been synthesized, where is tris(2-pyridylmethyl)amine and DBC is 3,-di-tert-butylcatecholate dianion. The TPA with complex reacts with O2 within minutes to afford intradiol cleavage, in 98% yield, which is the highest convesion obsesrved of all [Fe(L)DBC] complexes studied. More interestingly, the TPA complex is the fastest reacting of all the [Fe(L)DBC] complexes studied. Kinetic studies of the reaction of the complex with 1 atm of O2 in DMF under pseudo-first-order- conditions show that the TPA complex react appproximately three orders of magnitude faster than the corresponding NTA complex, where NTA is N,N- bis(carboxymethyl)glycine. Both the high specificity and the fast kinetics can be associated with the high Lewis acidity of athe ferric center in the TPA complex. To investigate the factors determining reactivity, we have solved the crystal structure of [Fe(TPA)DBC]BPh4 (space group P1̄ a = 12.464 (5) ̊, b = 13.480 (6) ̊, c = 15.980 (8) ̊, α = 85.11 (4)°, β =83.96 (4)°, γ ?? 70.76 (4)° V = 2517 (4) ̊3, Z = 2, R = 0.054 and Rw = 0.063). Compared with other complexes in the [Fe(L)DBC] series, the iron-catecholate interaction in the TPA complex is significantly stronger, resulting in the enhanced covalency of the metal-catecholate bonds and low-energy catecholate LMCT bands. The enhanced covalency is reflected by the isotropic shifts exibited by the DBC protons, which indicate increased semiquinone character. The greater semiquinone character in the TPA complex correlates well its high reactivity toaward O2. These trends provide substantial evidence for the substrate activitation mechanism proposed for the oxidative cleavage of catechols.

AB - [FeIII(TPA)DBC]BPh4, a new functional model for the catechol dioxygenases, has been synthesized, where is tris(2-pyridylmethyl)amine and DBC is 3,-di-tert-butylcatecholate dianion. The TPA with complex reacts with O2 within minutes to afford intradiol cleavage, in 98% yield, which is the highest convesion obsesrved of all [Fe(L)DBC] complexes studied. More interestingly, the TPA complex is the fastest reacting of all the [Fe(L)DBC] complexes studied. Kinetic studies of the reaction of the complex with 1 atm of O2 in DMF under pseudo-first-order- conditions show that the TPA complex react appproximately three orders of magnitude faster than the corresponding NTA complex, where NTA is N,N- bis(carboxymethyl)glycine. Both the high specificity and the fast kinetics can be associated with the high Lewis acidity of athe ferric center in the TPA complex. To investigate the factors determining reactivity, we have solved the crystal structure of [Fe(TPA)DBC]BPh4 (space group P1̄ a = 12.464 (5) ̊, b = 13.480 (6) ̊, c = 15.980 (8) ̊, α = 85.11 (4)°, β =83.96 (4)°, γ ?? 70.76 (4)° V = 2517 (4) ̊3, Z = 2, R = 0.054 and Rw = 0.063). Compared with other complexes in the [Fe(L)DBC] series, the iron-catecholate interaction in the TPA complex is significantly stronger, resulting in the enhanced covalency of the metal-catecholate bonds and low-energy catecholate LMCT bands. The enhanced covalency is reflected by the isotropic shifts exibited by the DBC protons, which indicate increased semiquinone character. The greater semiquinone character in the TPA complex correlates well its high reactivity toaward O2. These trends provide substantial evidence for the substrate activitation mechanism proposed for the oxidative cleavage of catechols.

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