Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Synthesis and Characterization of the Mixed-valence $[Fe^{II}Fe^{III}BPLNP(OAc)_2](BPh_4)_2$ Complex As a Model for the Reduced Form of the Purple Acid Phosphatase

  • Published : 20001000
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Abstract

[Fe II Fe III $BPLNP(OAc)_2](BPh_4)_2$ (1), a new model for the reduced form of the purple acid phosphatases, has been synthesized by using a dinucleating ligand, 2,6-bis[((2-pyridylmethyl)(6-methyl-2-pyridylmethyl)ami-no)methyl]-4-nitrophenol (HBPLNP) . Complex 1 has been studied by electronic spectral, NMR, EPR, SQUID, and electrochemical methods. Complex 1 exhibits two strong bands at 498 nm $(\varepsilon=$ 2.6 ${\times}10^3M-^1cm-^1)$ and 1363 nm $(\varepsilon=$ 5.7 ${\times}10^2M-^1cm-^1)$ in $CH_3CN.$ These are assigned to phenolate-to-FeIII and intervalence charge-transfer transitions, respectively. NMR spectrum of complex 1 exhibits sharp isotropically shifted resonances, which number is half of those expected for a valence-trapped species, indicating that electron transfer between FeⅡ and FeⅢ centers is faster than NMR time scale at room temperature. Complex 1 undergoes quasireversible one-electron redox processes. The $FeIII_2/FeIIFeIII$ and $FeIIFeIII/FeII_2$ redox couples are at 0.807 and 0.167 V ver-sus SCE, respectively. It has Kcomp = 5.9 ${\times}$10 1s(acetato) ligand combination sta-bilizes a mixed-valence FeIIFeIII complex in the air. Interestingly, complex 1 exhibits intense EPR signals at g = 8.56, 5.45, 4.30 corresponding to mononuclear high-spin FeⅢ species, which suggest a very weak magnetic coupling between the iron centers. Magnetic susceptibility study shows that there is a very weak antiferromag-netic coupling (J = $-0.78cm-^1$, H = $-2JS_1${\times}$S_2)$ between FeII and FeIII centers. Thus, we can suggest that complex 1 has a very weak antiferromagnetic coupling between the iron centers due to the electronic effect of the nitro group in the bridging phenolate ligand.

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