Carbon 13 chemical shifts paramagnetic compounds

Carbon Chemical Shifts. In general, because carbon chemical shift values are dominated by the paramagnetic term, they are sensitive to a variety of factors such as hybridization, inductive, electric field, steric , resonance, and neighboring anisotropic effects. In many instances trends can be found for a series of compounds, but interpretation of the results is difficult. Therefore, it can be more enlightening to simply look for where changes in chemical shift do and do not occur and correlate them to better characterized data. 

The usual carbon-) 3 chemical shift range of organic compounds ( 250 ppm) considerably expands in organometallic compounds. Paramagnetic metals in metallocenes (Table 4.72) induce particularly large 13C shift values [476]. 

Chemical shifts have been reported for [Me3CCH2HgX] 203) (see Table XII), tr-allylic derivatives (see Table XIII), o-cyclopentadienyl derivatives (see Table XIV), and miscellaneous compounds (see Table XV). In the case of fluxional a-cyclopentadienyl derivatives, it has been shown that chemical shifts can be used to differentiate between fluxional o-cyclopentadienyl derivatives and w-cyclopentadienyl derivatives 103). The NMR spectrum of [Sb(cyclopropyl)s] has only two carbon resonances, showing that the molecule is fluxional (56) and the NMR spectrum of the naturally occurring organometallic compound, 5 -deoxyadenosylcobalamin, has been reported (65). For a number of norbornane and allylic derivatives of palladium and platinum, a number of linear relationships have been found between chemical shifts of various carbon atoms. It was suggested that a term due to paramagnetic shielding by the metal was dominant 52b). 

The calculations allow some useful conclusions as to chemical influences on the shifts, e.g., a large part of the shifts in CHsX compounds, when X is CH3, NH2, OH, or F, depends on the increase in the paramagnetic terra with contraction of the carbon orbitals as charge is withdrawn by X (i.e., as increases). 

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