To begin our investigation, we first prepared the well-known silylamide [Co(TMSA)2]2 (1), following the procedure described by Power and co-workers (Scheme 1). Additionally, following a similar protocol the 2,2,5,5-tetramethyl-1,2,5-azadisilolidinyl ligated congener [Co(TMADS)2]2 (2), was obtained by facile salt metathesis reaction of CoCl2 and two equivalents of the respective lithiated silylamide in Et2O. In both cases, removal of solvent from the dark green solutions was followed by extraction with pentane, and subsequent purification by vacuum distillation. The previously reported silylamide 1 and the hitherto unreported 2 formed dark yellow to green vapors that solidified as dark red to dark brown chunks. We were also able to obtain X-ray quality crystals of 2 which confirmed its solid-state structure (further discussed below). In both cases volatilization occurred concomitant to fractional decomposition of the crude products. The resolidified distillates were then recrystallized from pentane to yield the two title compounds in yields of ca. 75% (1) and ca. 35% (2); the lower yield is likely due to increased thermal decomposition during distillation. The effective magnetic moment (μeff in Bohr magneton μB) of the dimeric cobalt compounds 1 and 2 was estimated using the Evans' method (Table ). This resulted in values of 5.56 μB and 5.32 μB, respectively. Following the preparation of the dimeric compounds, we speculated that we could break the μ-amido bridging bonding motif via addition of ligands that would coordinatively saturate the cobalt center to yield monomeric complexes. It should be noted that the synthesis and crystal structure of the BPY adduct 5 has been previously reported, yet information on its thermal properties were not provided. Prior to single-crystal X-ray diffraction (SC-XRD) analysis, we hypothesized that bidentate chelation should not occur. However, elemental analysis revealed only one DAD ligand per cobalt center.