Metallacyclobutadienes (MCBD) are critical intermediates in alkyne metathesis (AM) reactions that can facilitate the formation of carbon-carbon triple bonds or conjugated double bonds. The utility of these reactions has led to advances in late-stage total synthesis, macrocycle synthesis, and in the formation of conjugated polymers. However, these MCBD intermediates are challenging to access and have been only isolated on heavier transition metal complexes, which have limited their use in practical synthetic applications. Herein, we describe the synthesis of MCBDs on first-row transition metal complexes through a variety of streamlined approaches. These MCBDs were investigated through a variety of spectroscopic and crystallographic techniques to identify the electronic, magnetic, and structural information of the systems. The results from these studies show that first-row MCBDs exhibit reversible one-electron chemistry which has yet to be reported for other MCBD systems. Additionally, the MCBD could undergo a structural rearrangement to gain access to a metallatetrahedrane (MTd) species, which is another key intermediate in AM reactions. Furthermore, we have designed deprotiometallacyclobutadiene (dMCBD) complexes, which were found to be a key species in the formation of cyclic conjugated polymers. Moreover, we have designed heteroatom containing MCBDs (HMCBD) and these species were compared to all carbon based MCBDs with electronic, magnetic, structural, and theoretical studies to elucidate the key chemical features of these systems. These studies provide the chemistry community with easy access to molecules that are catalysts in the formation of cyclic conjugated polymers. These polymers have drastically different properties than their linear analogue, and so they are of interest to polymer and material scientists alike. Moreover, by inspecting the electronic and magnetic situation of these MCBD and their related motifs we can predict and propose molecules that can be synthesized from these systems and that can be used in productive synthetic applications.