THE INFRARED AND THE NEAR-ULTRAVIOLET ABSORPTION SPECTRA OF POLYPHENYL DERIVATIVES OF THE ELEMENTS OF GROUPS IVb AND Vb

Abstract

The near-ultraviolet absorption spectra of polyphenyl derivatives of the IVb and Vb elements have been studied in detail. In the case of the triphenyl derivatives of the Vb elements, the unshared p-electrons on the central atoms interact strongly with the π-orbitals of the benzene rings. When the central atoms do not possess unshared electrons as in the case of the derivatives of the IVb and the pentavalent Vb elements, there appears to be no such resonance interaction. The Hammett reactivity constants of the para- and meta-trityl, triphenylsilyl, and triphenylgermanyl groups are estimated to be close to zero. However, the reactivity constant of the triphenylsilyl group in the para position of phenol is estimated to be about 0.30. The infrared spectra of the phenyl derivatives of the IVb and Vb elements show smooth trends due to mass effects of the central atoms, in the C=C skeletal, C—H out-of-plane, and other vibrations. The absorption frequencies which are assigned to the phosphorus-phenyl and silicon–phenyl bonds in the literature do not appear to be unique for these linkages.