TY - JOUR
T1 - Role of the axial ligand in heme-CO backbonding; DFT analysis of vibrational data
AU - Vogel, Kathleen M.
AU - Kozlowski, Pawel M.
AU - Zgierski, Marek Z.
AU - Spiro, Thomas G.
N1 - Funding Information:
This work was supported by NIH grant HL 33576 from the National Institute of General Medicinal Science. Issued as NRCC No. 00000.
PY - 2000
Y1 - 2000
N2 - The FeCO backbonding correlation, a plot of C-O versus Fe-CO vibrational frequencies, is a useful tool for investigating proximal ligand and distal environmental effects in CO adducts of heme proteins and models. The data fall on parallel lines of negative slope, shifted along the Fe-CO axis for proximal ligands of different donor strength. However, new resonance Raman spectra of five-coordinate Fe(II)(porphyrins)(CO) with electron-withdrawing or -donating substituents reveal that the backbonding slope is reduced in the absence of a proximal ligand. This phenomenon has been explored with non-local density functional theory on Fe(II)(porphines)(CO) with fluorine, chlorine and amino substituents. The calculations likewise give lines of negative slope, displaced according to trans ligand donor strength. Strikingly, the slopes are nearly the same for pyridine and methylthiolate trans ligands, but halved for five-coordinate complexes, as in the experimental plots. However, the magnitude of the slopes, as well as the displacements of the correlations, are about twice the experimental values. The origin of the backbonding behavior can be seen in the bond-length relationships for the calculated structures. For a given C-O length, the Fe-CO bond is lengthened systematically by increasing the donor strength of the axial ligand, whose sigma donor orbital competes with the CO donor sigma orbital for the vacant Fe d(z2) orbital. For a given proximal ligand, the Fe-CO and C-O bond lengths are negatively correlated, as expected for backbonding. In addition, the slopes increase systematically with increasing ligand donor strength, because the longer Fe-CO distance decreases the π overlap, and increases the Fe-CO sensitivity to backbonding changes. (C) 2000 Elsevier Science S.A.
AB - The FeCO backbonding correlation, a plot of C-O versus Fe-CO vibrational frequencies, is a useful tool for investigating proximal ligand and distal environmental effects in CO adducts of heme proteins and models. The data fall on parallel lines of negative slope, shifted along the Fe-CO axis for proximal ligands of different donor strength. However, new resonance Raman spectra of five-coordinate Fe(II)(porphyrins)(CO) with electron-withdrawing or -donating substituents reveal that the backbonding slope is reduced in the absence of a proximal ligand. This phenomenon has been explored with non-local density functional theory on Fe(II)(porphines)(CO) with fluorine, chlorine and amino substituents. The calculations likewise give lines of negative slope, displaced according to trans ligand donor strength. Strikingly, the slopes are nearly the same for pyridine and methylthiolate trans ligands, but halved for five-coordinate complexes, as in the experimental plots. However, the magnitude of the slopes, as well as the displacements of the correlations, are about twice the experimental values. The origin of the backbonding behavior can be seen in the bond-length relationships for the calculated structures. For a given C-O length, the Fe-CO bond is lengthened systematically by increasing the donor strength of the axial ligand, whose sigma donor orbital competes with the CO donor sigma orbital for the vacant Fe d(z2) orbital. For a given proximal ligand, the Fe-CO and C-O bond lengths are negatively correlated, as expected for backbonding. In addition, the slopes increase systematically with increasing ligand donor strength, because the longer Fe-CO distance decreases the π overlap, and increases the Fe-CO sensitivity to backbonding changes. (C) 2000 Elsevier Science S.A.
KW - Backbonding
KW - Carbon monoxide
KW - Density functional theory study
KW - Heme
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U2 - 10.1016/S0020-1693(99)00253-4
DO - 10.1016/S0020-1693(99)00253-4
M3 - Article
AN - SCOPUS:0033806397
SN - 0020-1693
VL - 297
SP - 11
EP - 17
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
IS - 1-2
ER -