Substituent Effects on 15N and 17O NMR Chemical Shifts in 4′-Substituted trans-NNO-Azoxybenzenes

15N and 17O NMR spectra have been measured for a series of 4′-substituted trans-NNO-azoxybenzenes (AZOXY) and the obtained substituent chemical shift (SCS) values have been analyzed by means of the LSFE equation. Both the resonance and the polar contribution of substituents are important in determining the 15N(β) SCS and the adjacent terminal 17O SCS in the –Nα=Nβ(O)– function of the AZOXY set. The resonance contributions of the AZOXY sets differ from those of the corresponding PYNO sets in view of a depressed pi-acceptor resonance contribution. That is, the resonance susceptibility ratio in the LSFE equation, ρπ+⁄ρπ−, varies from 1.4 (PYNO) to 2–4 (AZOXY) for both 15N and 17O SCS. The results are compared with the 13C SCS of the corresponding positions in the relevant aromatic side-chain systems, and characterized in terms of repulsive pi-acceptor interaction between the substituents and the side-chain pi-electron systems. The importance of such dual resonance susceptibility has been shown for understand...

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