ESEEM and Mössbauer studies of the ferriheme model compound bis(3-aminopyrazole)tetraphenylporphyrinatoiron(III) chloride, [TPPFe(NH2PzH)2]Cl.

Abstract

A model heme complex, bis(3-aminopyrazole)tetraphenylporphinatoiron(III) chloride, [TPPFe (NH2PzH)2]Cl, for which the EPR g-values lead to a rhombicity V/delta = 1.2 if gzz is the largest g-value, have been investigated by electron spin echo envelope modulation (ESEEM) and Mössbauer spectroscopies. The ESEEM studies focus on the proton sum frequency peaks at near twice the proton Larmor frequency. Analysis of the distant proton peak (mainly due to the pyrrole-H) at exactly twice the proton Larmor frequency shows conclusively that gzz is aligned along the normal to the porphyrin plane, and thus the electron configuration is (dxy)2(dxz,dyz)3, with gzz > gyy > gxx. This system is thus another violation to Taylor's "proper axis system" rule. The near proton (the alpha-H and N-H of the axial ligands) peaks provide distance information for those protons from the metal. Magnetic Mössbauer studies of the same complex confirm the (dxy)2(dxz,dyz)3 ground state and indicate that, as is the case for cytochrome P450cam, Axx is the largest magnitude A-value, and is negative in sign. Other low-spin iron(III) porphyrinates also have Axx of negative sign, but usually the magnitude is only about half that of Azz, which is always positive in sign.