Electron Spin Resonance of Fe(CN)5NO3− and Fe(CN)5NOH2−

Abstract
It has been shown by means of ESR in aqueous, nonaqueous, and aprotic solution as well as in irradiated single crystals in the temperature range of 77°—300°K, that two paramagnetic species are obtained by reduction of pentacyanonitrosoferrate(II) which are in a protonation—deprotonation equilibrium. In support of the ESR data, electronic spectra have been investigated and pKa values have been determined by acidimetry and spectrophotometry. The spin density was calculated from ESR data of nFe(CN)5NO3− for n=56, 57 isotopes and found to be consistent with the lowest antibonding orbital being mainly π*NO.

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