Ever since Alfred Werner coined the term coordination complex in 1893, and was able to exemplify his far-reaching theory using the example of hexol in 1911, the coordination chemistry of the later transition metal cobalt (Co) expanded vastly and has been subject of extensive research. Among the many compound classes known to date, there are Co(II) (silyl)amides, pyrrolates and aminopyridinates. With our long-term research focusing on the synthesis of inorganic complexes and their evaluation as precursors for the application in chemical gas phase deposition processes such as metal organic chemical vapor deposition (MOCVD) and atomic layer deposition (ALD), and our recent interest in the chemistry of the later transition metal Co, we identified prior mentioned classes as promising model systems for our studies. Even though operational modes and conditions of MOCVD and ALD processes differ, their complementary and precise applicability for the deposition of a broad range of thin film materials have made them industrially indispensable in fields like microelectronics, optoelectronics and photovoltaics. Choosing the right precursor, namely a compound that is volatilized during the process to serve as chemical source for the target material, for a specific application is of crucial importance hereby: The precursor needs to meet demanding requirements such as high thermal stability, sufficient volatility, high but controllable reactivity and lastly non-etching behavior. Reviewing the list of commonly used Co precursors, it becomes apparent that all-nitrogen or predominantly nitrogen coordinated compounds are widely unexplored in terms of their general suitability as precursors and in terms of actual CVD/ALD process development. This is surprising as the two allnitrogen coordinated precursors Co(II) bis-(di-tert-butyl-acetamidinate), and Co(II) bis-(ditert-butyl-diazadienyl) (Co(DAD)2) have led to significant advancements in ALD and material science. While the likely best known Co(II) silylamide [Co(N(SiMe3)2)2]2 in the following referred to as [Co(TMSA)2]2 has not found application in this field yet, the recent usage of its Lewis base coordinated congener [Co(TMSA)2(THF)] in ALD raises the question if all-nitrogen Lewis adducts of the type [Co(TMSA)2L] could be viable precursor candidates. In this regard, it is noteworthy, that a number of Co(II) silylamides and Lewis adducts adapted from them have already been studied in recent years in terms of their structural, electronic and magnetic properties. Beginning with [Co(TMSA)2]2, Power and coworkers hereby focused on the synthesis and bonding characterization of low-coordinate Co(II) silylamides of the type [Co(TMSA)2L], and [Co(N(SiMe3)Dipp)L], with Dipp being 2,6diisopropylphenyl and L being a series of Lewis bases ranging from THF and pyridine to several phosphines derivates. Complementing these efforts, Rabu and coworkers, as well as Layfield and coworkers, employed carbenes as Lewis bases and brought three-coordinate complexes of the type [Co(TMSA)2(NHC)] into focus. While Layfield studied the rearrangement of the coordinating carbene, Rabu demonstrated well controllable transamination reactions of [Co(TMSA)2(NHC)] type complexes in interplay with the sterically demanding primary amine (Dipp)NH2. Typically, (silyl)amide ligands with considerable molecular weight and steric demand were employed to stabilize the Co(II) ion in these reports.