The electron transmission and dissociative electron attachment spectra of the 1-chloroalkyl benzene derivatives, C6H5(CH2)(3)Cl and C6H5(CH2)(4)Cl, and of the sulfur and silicon derivatives, C6H5SCH2Cl, C6H5Si(CH3)(2)CH2Cl and C6H5CH2Si(CH3)(2)CH2Cl, 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 C6H5(CH2)(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 C6H5(CH2)(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.