Transition metal complexes with metal-ligand multiple bonds have been proven to perform critical transformations such as the conversion of dinitrogen to ammonia, activation of methane to borylated products, and metathesis polymerization reactions. In this context, the functionality of metal-carbon, metal-pnictogen, and metal-chalcogen multiple bonds have been vigorously explored due to the potential for molecular applications in unusual bond transformations. This work will focus on the synthesis, reactivity, spectral characterization, and computational elucidation of rare metal-ligand multiple bonds of group V transition metals and exploration of products formed in the reactivity of these complexes. The first chapter will introduce the synthesis of a rare vanadium methylidene complex, its reactivity with CH3+ in the formation of ethylene, and the activation of N2 using a transient vanadium imido. The second chapter will cover the chemistry of the sodium phosphaethynolate anion, NaOCP, in the isolation of a terminal and mononuclear niobium phosphide. The third chapter will cover the chemistry of white phosphorus, P4, in the isolation of a unique tricyclic P6 framework spanning two vanadium centers and a terminal vanadium phosphido. The fourth chapter will cover the synthesis of a terminal niobium nitride utilizing a redox active ligand and NaN3 as the N-atom source. Finally, the last chapter will introduce the synthesis and characterization of group V metal telluride complexes using an easy-to-prepare telluride atom transfer reagent, lithium tellurolate. Access to a triad of bistelluride systems for group V metals has allowed us to compare them using a combination of theory and spectroscopy including Te-L1 edge XANES