Deprotonation of the new (R = propyl, 3,5-Me2Ph) and previously prepared (R = 2,4,6-Me3Ph, 2,6-(Pr2Ph)-Pr-i, 3,5(CF3)(2)Ph) symmetrical diamidosilyl ether ligand precursors {[RNHSiMe2](2)O} with 2 equiv of (BuLi)-Bu-n in THF resulted in a new class of mixed-donor amido-amino-siloxo ligands of the form {RNLiSiMe2N(R)SiMe2OLi} (R= propyl (1c), 3,5-Me2Ph (2c), 2,4,6-Me3Ph (3c), 2,6-(Pr2Ph)-Pr-i (4c), 3,5-(CF3)(2)Ph (5c)) in one-step and high yield via a retro-Brook-type rearrangement mechanism. Ligands 1c, 3c, and 4c have been structurally characterized in the presence and absence of THF/ether donor solvents and exhibited a range of aggregated structures with ring-laddering, ring-stacking, and cubane motifs; higher-nuclearity clusters for base-free systems were observed for 1c and 4c. H-1, Li-7, and selected C-13{H-1} NMR spectra in THF-d(8) and toluene-d(8) are described; the Li-7 data are indicative of intramolecular fluxional behavior as a function of temperature but do not shed light on the nuclearity of the salts in solution. Reaction kinetics were investigated by variable-temperature H-1 NMR spectroscopy and showed that the rate of rearrangement reactions increases with decreasing steric hindrance and with increasing electron-donating ability of the R substituents, with tau(1/2) values ranging from 5.7 x 10(1) to 1.5 x 10(8) s for 2c and 5c, respectively.