Origin of 13C complexation shifts in the adduct formation of 2-butyl phenyl ethers with a dirhodium tetracarboxylate complex.
Complexation of the oxygen atom in 2-butyl phenyl ethers to a rhodium atom of the dirhodium tetracarboxylate Rh(II) 2[(R)-(+)-MTPA]4(Rh*, MTPA-H = methoxytrifluoromethylphenylacetic acid identical with Mosher's acid) deshields an sp3-hybridized 13C nucleus directly bonded to the ether oxygen; apparently, the inductive effect of the oxygen is enhanced when it is complexed to the rhodium atom. On the other hand, deshielding complexation shifts of aromatic ipso-carbons (alpha-positioned) are minute but ortho- and para-carbon signals are influenced by the resonance effect of oxygen. This effect can be modulated by further substituents at the benzene ring. In turn, this modulation of the resonance correlates linearly ith the magnitude of the inductive effect exerted on the aliphatic alpha-carbon atoms. Diastereomeric dispersion effects at 13C signals can be observed for most compounds, indicating that enantiodifferentiation is possible in this class of ethers.