Stoichiometric reaction of [Sm(Tp(Me2))2], 1, with a variety of reducible ketone- and quinone-type substrates gave thermally stable, isolable radical anions/ketyls in moderate to good yields. Thus reaction with benzophenone gave [Sm(Tp(Me2))(2)(OCPh2)], 2, with fluorenone [Sm(Tp(Me2))(2)(n(1)-OC13H8)], 3, and di-tert-butylparaqui none [Sm(Tp(Me2))(2)(eta(1)-OC6H2((BU)-B-t)(2)O)], 4, each of which was structurally characterized, In the case of the less-hindered benzoquinone, an unimetallic semiquinone [Sm(Tp(Me2))(2)(OC6H4O)], 5, could be isolated, although it was unstable with respect to formation of the dimetallic complex [Sm(Tp(Me2))(2)](2)(mu-OC6H4O), 6. Compound 6 was structurally characterized, as was its anthraquinone analogue [Sm(Tp(Me2))(2)](2)(mu-OC14H8O), 7. When the analogous reaction was carried out between the less-reducing [Eu(Tp(Me2))(2)] and benzoquinone, only the europium analogue of the semiquinone 5, [Eu(Tp(Me2))(2)-(OC6H4O)], 8, could be isolated. The use of the sterically hindered 3,5-di-terf-butyl-o-benzoqui none allowed isolation of [Sm(Tp(Me2))(2)(DTBSQ)], 9.