Tertiary arsines of the type Me2AsR [R = Et, Prn, Pri, Bun, Bui, But, allyl, Me3SiCH2, Ph, Bzl, mesityl, and p-tolyl] have been synthesized in excellent yields by alkylating Me2AsNMe2 with Grignard reagents. The utility of aluminum alkyls as alternative alkylating agents for certain arsines has also been demonstrated. All compounds have been characterized using IR, MS, and NMR spectroscopy. An NMR spectral analysis (1H, 13C, and 29Si) is given and these results are compared with those for the homoleptic arsines, R3AS. © 1992, Taylor & Francis Group, LLC. All rights reserved.