title: Intramolecular electron transfer in heterosubstituted benzene derivatives as probed by dissociative electron attachment.
abstract: The electron transmission and dissociative electron attachment spectra of the 1-chloroalkyl benzene derivatives, C(6)H(5)(CH(2))(3)Cl and C(6)H(5)(CH(2))(4)Cl, and of the sulfur and silicon derivatives, C(6)H(5)SCH(2)Cl, C(6)H(5)Si(CH(3))(2)CH(2)Cl and C(6)H(5)CH(2)Si(CH(3))(2)CH(2)Cl, are presented for the first time. The relative Cl(-) fragment anion currents generated by electron attachment to the benzene pi* LUMO are measured in the series C(6)H(5)(CH(2))(n)Cl, with n = 1-4, and in the heteroatomic compounds. The Cl(-) yield reflects the rate of intramolecular electron transfer between the pi-system and the remote chlorine atom, which in turn depends on the extent of through-bond coupling between the localized pi* and sigma*(Cl-C) orbitals. In compounds C(6)H(5)(CH(2))(n)Cl the Cl(-) current rapidly decreases with increasing length of the saturated chain. This decrease is significantly attenuated when a carbon atom of the alkyl skeleton is replaced with a third-row heteroatom. This greater ability to promote through-bond coupling between the pi* and sigma*(Cl-C) orbitals is attributed to the sizably lower energy of the empty sigma*(S-C) and sigma*(Si-C) orbitals with respect to the sigma*(C-C) orbitals. In the sulfur derivative the increase of the Cl(-) current is larger than in the silicon analogue. In this case, however, other negative fragments are observed, due to dissociation of the S-C bonds.
authors.affiliation: Dipartimento di Chimica G. Ciamician, Università di Bologna, via Selmi 2, 40126 Bologna, Italy. modelli@ciam.unibo.it
authors.forename: Alberto
authors.initials: A
authors.lastname: Modelli
authors.forename: Marco
authors.initials: M
authors.lastname: Venuti
authors.forename: László
authors.initials: L
authors.lastname: Szepes
mesh_terms: D001555:Benzene Derivatives / Q000737:chemistry*; D004583:Electrons; D008968:Molecular Conformation; D011789:Quantum Theory; D013057:Spectrum Analysis; D013816:Thermodynamics
chemical_list: D001555:Benzene Derivatives