Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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A New Functional Model Complex of Extradiol-cleaving Catechol Dioxygenases: Properties and Reactivity of [$Fe^{II}$(BLPA)DBCH]BPh₄

  • Published : 1999.12.20
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Abstract

[Fe$^{II}$(BLPA)DBCH]BPh₄ (1), a new functional model for the extradiol-cleaving catechol dioxygenases, has been synthesized, where BLPA is bis(6-methyl-2-pyridylmethyl)(2-pyridylmethyl)amine and DBCH is 3,5-di-tert-butylcatecholate monoanion. ¹H NMR and EPR studies confirm that 1 has a high-spin Fe(II) (S = 2) center. The electronic spectrum of 1 exhibits one absorption band at 386 nm, showing the yellow color of the typical [Fe$^{II}$(BLPA)] complex. Upon exposure to O₂, 1 is converted to an intense blue species within a minute. This blue species exhibits two intense bands at 586 and 960 nm and EPR signals at g = 5.5 and 8.0 corresponding to the high-spin Fe(III) complex (S = 5/2, E/D = 0.11). This blue complex further reacts with O₂ to be converted to (μ-oxo)Fe$^{III}_2$ complex within a few hours. Interestingly, 1 affords intradiol cleavage (65%) and extradiol cleavage (20%) products after the oxygenation. It can be suggested that 1 undergoes two different oxygenation pathways. The one takes the substrate activation mechanism proposed for the intradiol cleavage products after the oxidation of the $Fe^II\;to\;Fe^{III}$. The other involves the direct attack of O₂ to $Fe^{II}$ center, forming the $Fe^{III}$-superoxo intermediate which can give rise to the extradiol cleavage products. 1 is the first functional Fe(II) complex for extradiol-cleaving dioxygenases giving extradiol cleavage products.

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