Publication

Journal	Physical Chemistry Chemical Physics
Volume (Issue)	17
Page(s)	4696
Title of proceedings	Physical Chemistry Chemical Physics
DOI	10.1039/c4cp04083j

URL	http://homeweb.unifr.ch/allanm/pub/ma/dir_allan/Regeta_cyclooctenes_PCCP_2015.pdf
Type of Open Access	Website

The effect which deformation of the double bond in trans-cyclooctene (TCO), compared to cis-cyclooctene (CCO), has on its negative ion – and indirectly on the p* virtual orbital – was studied by electron-impact spectroscopy. Differential elastic and vibrational excitation cross sections were measured at a scattering angle of theta = 135°. The vertical attachment energy (VAE) derived from the vibrational excitation spectra is 1.87 eV in TCO, only 0.09 eV lower than in the unstrained CCO, 1.96 eV. The substantial deformation of the CQC bond in TCO thus stabilizes its transient negative ion by a surprisingly small amount and this effect is ascribed in part to the Pauli (steric) destabilization of the TCO p* orbital by the alkyl chain facing the pi* lobes. An interesting effect is observed in the elastic cross section which is about 45% larger for TCO at low energies (0.4 eV), despite the similar geometrical size of the two molecules. Ramsauer–Townsend minima are observed in the elastic cross section at 0.13 and 0.12 eV for CCO and TCO, respectively. Implications of the findings on enhancement of the dienophile capacity of TCO are discussed.