Thus it is consequential that an assessment of the thermal properties of these types of compounds was not a main objective until now. This is likewise applicable to Co(II) pyrrolate and aminopyridinate complexes of which a few examples have been reported but never been compared in terms of structure and thermal properties. Aiming to broaden the knowledge on selected Co(II) (silyl)amides and some of their Lewis adducts as well as Co(II) pyrrolates and aminopyridinates, this study provides a detailed survey over and comparison of the manifold structural chemistry of in total eleven complexes. First, utilizing the silylamide ligand 2,2,5,5-tetramethyl-1,2,5-azadisilolidinyl, a close structural relative to [Co(TMSA)2]2 is presented. Novel Lewis adducts of the latter with N,N'-di-tertbutylethane-1,2-diimine, N,N-dimethylpyridine-2-amine and N-tert-butyl-1-(pyridine-2yl)methaneimine are reported that broaden the number of all-nitrogen low-coordinate Co(II) silylamides. Furthermore, a straightforward and simplified protocol for the synthesis of two related Co(II) pyrrolates by transpyrrolylation of [Co(TMSA)2]2 is described. Hereby, the title compounds, chelated by the N,N'-2-(dimethylaminomethyl)pyrrolyl, and N-2-(tertbutyliminomethyl)pyrrolyl ligand, have been reported prior but not yet been compared in terms of structure and thermal properties. Sharing a chelating nature, the two amido-amino ligands N,N-dimethyl(N'-tert-butyl)ethane-1-amino-2-amide and N,N-dimethyl(N'trimethylsilyl)ethane-1-amino-2-amide are moreover employed to synthesize novel 4-fold coordinated Co(II) amide complexes with distorted tetrahedral geometry. For one of them, the complete absence of silicon in the ligand sphere renders a rare example and has not been reported for amido-amino ligands of comparable size to the best of our knowledge. Lastly, a rare example of a homoleptic, binuclear Co(II) aminopyridinate complex with a four-fold and a five-fold coordinated Co(II) atom surrounded by four 4-methyl-N-(trimethylsilyl)pyridine-2amido ligands is described. The synthesis and solid state structures, obtained from single crystal X-ray diffractometry (SC-XRD), of in total eight of the title compounds are reported for the first time. Owing to their respective ligand systems and binding modes, the compounds are divided into four structural categories which allows the identification of multiple similarities and differences that are found to directly affect their thermal stability and volatility in thermogravimetric analysis (TGA) and bulk sublimation experiments. Thus, the present study offers a first structure -thermal property correlation that may be built upon for future, increased exploration of Co(II) (silyl)amides and related compounds as precursors for chemical gas phase deposition.