Abstract The first ionization potentials of 11 silylmethyl-substituted amines R 3− n N (CH 2 Si (CH 3) 3) n as determined photoelectron spectroscopy range from 9.07 eV to 7.66 eV. The most easily ionized molecule, N (CH 2 Si (CH 3) 3) 3, can also be oxidized with AlCl 3 in H 2 CCl 2 solution to its aminium radical cation. The ESR spectra recorded between 180 K and 310 K display a strong temperature dependence due to rotations around the> N CH 2 ...