Issue 12, 1989

Hel photoelectron studies of unstable ketenes: mono- and di-phenylketenes, and their gas-phase conformations

Abstract

Hel photoelectron spectra are reported for the semistable mono- and di-phenylketene molecules generated in high yield by in situ metal dehalogenation reactions of the appropriate chlorophenylsubstituted acid chlorides. The photoelectron results can be interpreted through a simple perturbation approach, and in conjunction with semiempirical MNDO and AM1 calculations provide gas-phase structural evidence for a planar π-conjugated monophenylketene molecule, and a non-planar diphenylketene species in which both phenyl groups are rotated, in a conrotatory fashion, some 30–40° out of the [graphic omitted]C[double bond, length half m-dash]C[double bond, length half m-dash]O π system. The limitations of the MNDO method and the greater reliability of AM1 for the assessment of the relative energies of rotational conformers is discussed. HAM/3 calculations are in excellent agreement with the experimental ionisation potentials.

Article information

Article type
Paper

J. Chem. Soc., Perkin Trans. 2, 1989, 1987-1992

Hel photoelectron studies of unstable ketenes: mono- and di-phenylketenes, and their gas-phase conformations

R. Sammynaiken and N. P. C. Westwood, J. Chem. Soc., Perkin Trans. 2, 1989, 1987 DOI: 10.1039/P29890001987

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