When unsaturated substrates are brought into proximity to metal carbon multiple bonds, a diverse set of reactivity generally ensues. Pioneering work in polymerization and metathesis chemistry has allowed chemists to design new synthetic pathways for complex molecules, such as natural products and value-added chemicals. However, many of these influential systems rely on late transition metals. This presentation will outline the interesting binding modes of a variety of unsaturated substrates to rarely reported vanadium alkylidynes and titanium alkylidenes. These molecules exhibit novel geometric rearrangements when the coordination environment around the metal center is perturbed. This rearrangement is reminiscent of proposed transition states of metathesis and polymerization reactions. Molecules that will be presented are a vanadium ynamide, a vanadium azaallene, a titanium azaallene, and a titanium ketenimines, to name a few. These unique structural motifs will be discussed as potential complexes involved in polymerization reactions.

Early transition metal multiple bonds and their reactivity with unsaturated substrates

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ACS Fall 2022

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