TY - JOUR
T1 - Correlation of Carbon-13 and Oxygen-17 Chemical Shifts and the Vibrational Frequency of Electrically Perturbed Carbon Monoxide
T2 - A Possible Model for Distal Ligand Effects in Carbonmonoxyheme Proteins
AU - Augspurger, Joseph D.
AU - Dykstra, Clifford E.
AU - Oldfield, Eric
PY - 1991
Y1 - 1991
N2 - Ab initio calculations have been carried out that demonstrate an essentially linear correlation between the vibrational frequency of carbon monoxide and its carbon-13 and oxygen-17 chemical shifts, under a variety of external electrical influences. However, the correlations for carbon-13 and oxygen-17 shifts turn out be in opposite directions. Electronic structure calculations reveal that it is polarization of the electron charge density along the intermolecular axis that changes the chemical shielding oppositely for the carbon and oxygen nuclei. Recent experiments have pointed to just such a correlation in a wide range of carbonmonoxyheme proteins, and so electrical perturbation is a possible cause of distal ligand effects. Furthermore, the experimentally determined correlation of the vibrational frequency with oxygen-17 quadrupole coupling constants is also seen in the calculations.
AB - Ab initio calculations have been carried out that demonstrate an essentially linear correlation between the vibrational frequency of carbon monoxide and its carbon-13 and oxygen-17 chemical shifts, under a variety of external electrical influences. However, the correlations for carbon-13 and oxygen-17 shifts turn out be in opposite directions. Electronic structure calculations reveal that it is polarization of the electron charge density along the intermolecular axis that changes the chemical shielding oppositely for the carbon and oxygen nuclei. Recent experiments have pointed to just such a correlation in a wide range of carbonmonoxyheme proteins, and so electrical perturbation is a possible cause of distal ligand effects. Furthermore, the experimentally determined correlation of the vibrational frequency with oxygen-17 quadrupole coupling constants is also seen in the calculations.
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U2 - 10.1021/ja00007a015
DO - 10.1021/ja00007a015
M3 - Article
AN - SCOPUS:0000435803
SN - 0002-7863
VL - 113
SP - 2447
EP - 2451
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 7
ER -