Eight new atomic layer deposition (ALD) precursors were synthesized using a ligand that is new to the field of ALD: (tBuNH)SiMe2NMe2. Complexes containing Mg, V, Mn, Fe, Co, Ni, and Zn were found to be tetrahedral, and Li complexes form more complex structures. These compounds performed exceptionally well by thermogravimetric analysis (TGA). All compounds except for one Li species and the Fe complex left residual masses below 5%, similar or better than the analogous amidinate complexes. In particular, the Co(II) complex is very thermally robust and performs very well during a TGA stress test, surpassing temperatures above 200 °C. These compounds are the first of a family of precursors containing this type of monoanionic N-Si-N ligand and are prime candidates for ALD process development.