Metal-ligand multiple bonds (MLMBs), characterized by a σ²π²-⁴ bonding scheme, play a crucial role in industrial and biological processes such as nitrogen fixation, polymerization, and fine chemical synthesis. While significant progress has been made in understanding MLMBs with lighter p-block elements, their heavier congeners remain underexplored due to synthetic challenges including the preparation of low-valent metal precursors and lack of efficient atom-transfer methodologies. Turning to the metal, much of the work surrounding MLMBs, especially for early transition metals, has been conducted on high-valent systems containing minimal metal-based electron density. Expanding synthetic strategies for heavier p-block MLMB motifs and for MLMBs on metal systems with metalloradical character enhances our understanding of chemical bonding and electronic structure of MLMB motifs while enabling access to novel reactivity and material precursors.Chapter 1 introduces MLMB motifs from a molecular orbital perspective with an emphasis on the nature of the chemical bond including the ability to localize electrons within a molecule to better understand spectroscopic features and reactivity. Additionally, a review of synthetic methodologies for the synthesis of metal pnictogen (N, P, As, Sb) multiple bonds is included. Chapters 2-4 focus on the reactivity of a low-valent TiII chloride system [(TptBu,Me)TiCl] (TptBu,Me = hydridotris(3-tert-butyl-5-methylpyrazol-1-yl)borate) and its ability to undergo group transfer reactions with neutral reagents. Chapter 2 describes the synthesis and spectroscopic characterization of the first mononuclear TiIII imido, while Chapters 3 and 4 detail the investigation of steric and electronic factors governing various mechanisms of titanium imido synthesis. In contrast to [(TptBu,Me)TiCl], the low-valent TiII system [K(crypt)][(PN)2TiCl] (PN- = N-(2-(diisopropylphosphaneyl)-4-methylphenyl)-2,4,6-trimethylanilide; crypt = 2.2.2-cryptand) reacts via transmetallation for the synthesis of novel MLMB motifs. Chapter 5 details the synthesis and characterization of the first titanium, group 4, and first-row transition metal phosphorus and arsenic triple bonds providing insights into the nature of the chemical bond through an isostructural scaffold. Finally, Chapter 6 combines steric and electronic insights of MLMB systems with metalloradical character to uncover redox-induced reversible carbon dioxide capture utilizing a Ti≡O moiety.