Several silyl and alkaline metal substituted silylenes have been investigated using the CAS-ACPF method in conjunction with the aug-cc-pVTZ basis sets. Silylsilylene and disilylsilylene are found to have singlet ground states with Delta E(ST)(-)values of 0.676 and 0.319 eV, respectively. The adiabatic ground state electron affinities are found to be 1.572 and 2.361 eV for HSiSiH3 and Si(SiH3)(2). respectively. Both silylenes possesses a stable (2)A(1) excited negative ion state, with respective adiabatic EA values of 0.037 and 1.000 eV. In contrast, all silylenes with at least one akaline metal substituent exhibit triplet neutral ground states. The metalated silylenes HSiLi, HSiNa, LiSiSiH3, NaSiLi, SiLi2, and SiNa2 have adiabatic ground state EAs somewhat below 1 eV, but each of these negatively charged system possesses up to three bound excited negative ion states, some of which are dipole-bound states.