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Additional resources for Spectroscopic Methods in Bioinorganic Chemistry
33 populations of the four energy levels of Figure 1 are unequal, as determined by the Boltzmann distribution. Thus, the resulting resonance will not be at the diamagnetic position (the position marked by the dotted line in Figure 2), but rather either to higher or lower frequency (13\of the frequency of the same nucleus in the corresponding diamagnetic complex. The chemical shifts of the nuclei of the paramagnetic complex vary linearly with inverse temperature (usually—see the section on temperature dependence below) as a result of the expansion of the Boltzmann terms.
39,40) TjS should be measured before 2D experiments are attempted, in order to allow the investigator to optimize the experiment, as will be discussed below. Usually, those wishing to obtain NOESY and ROESY spectra of paramagnetic complexes would prefer to have their T^s be as long as possible, in order to allow time for NOEs to build up, and to achieve this it is always a good idea to purge the solution sample with argon or nitrogen in order to remove dissolved oxygen, which, because it is paramagnetic, shortens T s and T s by spin exchange.
Chem. 1997,36, 985-993. 11. inAdv. Inorg. Chem. , 1992, Vol. 38. pp 165-216. 12. ; Münck, E. J. Am. Chem. Soc. 1995, 117, 1169-1170. ; ACS Symposium Series; American Chemical Society: Washington, DC, 1998. Chapter 3 Advances in Single- and Multidimensional NMR Spectroscopy of Paramagnetic Metal Complexes F. Ann Walker Department of Chemistry, University of Arizona, Tucson, AZ 85721 l3 Proton (and C) N M R signals of paramagnetic metal complexes (and metalloproteins) can often, but not always, be detected by suitable modification of the standard experiments that are a part of the software of any modern N M R spectrometer.