John Oakes

Photoelectron spectroscopy of radical anions

Abstract The photoelectron spectroscopy of a number of radical anions has been investigated. We find the following electron affinities: EA(C3) =1.981 ±0.020 eV, EA(C3H) = 1.858 ±0.023 eV, EA(C3H2) = 1.794 ± 0.025 eV, EA(C3O) = 1.34±0.15 eV, EA(C3O2) = 0.85±0.15 eV, EA(C4O)= 2.05±0.15 eV, and EA(CS2) = 0.895± 0.020 eV. The structure and bonding for each of these ions is discussed.

The photoelectron spectroscopy of HO−2

The photoelectron spectroscopy of HO−2 and DO−2 has been studied. We find the electron affinities (E.A.) of the corresponding radicals to be E.A.(HO2)=1.078±0.017 eV and E.A.(DO2)=1.089±0.017 eV; the gas phase acidity of hydrogen peroxide is ΔH○acid (HO2–H) =376.4 ±0.6 kcal/mol. The electron spectra show only one active mode which we assign as the HO–O stretch (ω3). By modeling the Franck–Condon factors we deduce a molecular structure for the HO−2 ion: r0(HO–O)=1.50 A, r0(H–OO)=0.97 A, and ∠(H–O–O)=104°. A parallel set of GVB/PP, GVB‐CI, and POL‐CI ab initio electronic structure computations has been carried out for this ion.

Resolution and coupling of 1-(2′-hydroxy-1′-naphthyl)isoquinolines

Abstract The synthesis of bridged dimeric isoquinolylnaphthols has been developed. A simple method for the resolution of 1,1′-isoquinolyl-2′-naphthol permits measurement of the optical stability of the monomer, and in several cases slow racemisation at ambient temperature was observed. The enantiomeric stability is not greatly affected by steric buttressing. An unusual enhancement of the rate of atropisomerism is provided by the 3-bromomethylisoquinolines, and undermines the possibility of coupling pure enantiomeric components to provide a single stereoisomer of a tetradentate ligand.