Photoelectron Spectroscopy and Related Electrochemical Studies

Photoelectron Spectroscopy and Related Electrochemical Studies.—In a continuation of their studies of the conformational analysis of tetra-alkylhydrazines, the Wisconsin group have analysed the bridged hydrazines (11)—(15) by C n.m.r., photoelectron spectroscopy (p.e.s.), and cyclic voltammetry. Within this series, the measurement of E values by cyclic voltammetry is relatively uninformative with respect to conformation. Again the interpretation of the p.e.s. results is complex, but dynamic n.m.r. studies have clearly shown that (15) adopts only the endo-cis-tmed conformation whereas (11)—(13) are trans-tused. 

The important synthetic chemistry resulting in the ready availability of cyclic peroxides has led to p.e.s. studies of a number of these compounds. Information concerning conformation is available. For example, AE, the energy difference between the first two ionization potentials of peroxides, can be related to the 0—0 torsional angle f) by the equation AE/eV=2.08 cos -I- 0.15. Further aspects of peroxides are discussed below. 

The spectrum of the ether (16) has been compared to those of other tetramethylenenorbornanes. 

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