Jp. Simonato et al., An integrated approach to the mid-spin state (S=3/2) in six-coordinate iron(III) chiroporphryrins, INORG CHEM, 39(18), 2000, pp. 3978-3987
An intermediate-spin state very close to the mid-spin state (S = 3/2) can b
e stabilized in a ferric porphyrin by an integrated approach which combines
the favorable effects of a weak axial field strength and of a small macroc
ycle hole. Axial ligand exchange by reaction of chloroiron(III)tetramethylc
hiroporphyrin [(TMCP)FeCl] with silver perchlorate in ethanol-chloroform le
ads to ethanol-ligated ferric chiroporphyrins. Two distinct crystalline pro
ducts containing a bisethanol complex [[(TMCP)Fe-III(EtOH)(2)]ClO4] and thr
ee variants of a mixed ethanol-water complex [[(TMCP)Fe-III(EtOH)(H2O)]ClO4
] have been structurally characterized in the solid state. The small hole o
f the ruffled chiroporphyrin and the weak axial oxygen ligation result in s
trongly tetragonally distorted complexes. The sh-coordinate species exhibit
long axial Fe-O bond distances (2.173(5)-2.272(4) Angstrom) and the shorte
st equatorial Fe-N(av) distances (1.950(5)-1.978(7) Angstrom) found as yet
in a ferric porphyrin, reflecting a singly occupied d(z)(2) orbital and a l
argely depopulated d(x2-y2) orbital. An intriguing case of bond-stretch iso
merism is seen for the axial Fe-O bonds in two crystallographically indepen
dent mixed ethanol-water species, and it is accounted for by their distinct
intra- and intermolecular hydrogen-bond arrays. The Mossbauer spectrum (de
lta = 0.35(1) mm s(-1) and Delta E-Q = 3.79(1) mm s(-1) at 77 K) indicates
a strong tetragonal distortion around the ferric ion, in agreement with the
structural data. The value of the magnetic moment (mu(eff) = 3.8 mu(B) in
the range 50-300 K) strongly supports a mid-spin state (S = 3/2). The EPR s
pectrum at 80 K (g(perpendicular to) approximate to 4.0, g(parallel to) app
roximate to 2.00) is consistent with a nearly pure mid-spin state ((4)A(2))
With little rhombic distortion. The H-1 NMR spectra in CDCl3-EtOH exhibit
upfield-shifted resonances for the pyrrole protons (delta approximate to -3
0 ppm) which are consistent with the depopulated iron d(x2-y2) orbital. Sol
ution equilibria with water and various alcohols, and the spin state of the
corresponding species, are discussed on the basis of the NMR data. The bis
ethanol and ethanol-water species are potential models of unknown hemoprote
in ligation states such as Tyr(OH)/Tyr(OH) or Tyr(OH)/H2O that could be obt
ained by site-directed mutagenesis.