Catalysis is the second largest application for V after its use as an additive to improve steel production. Molecular complexes of vanadium(V) are particularly useful and efficient catalysts for oxidation processes; however, their ability to catalyze reductive transformations has yet to be fully explored. Here we report the first examples of polar organic functionality reduction mediated by V. Open-shell V-III complexes that feature a pi-radical monoanionic 2,2':6',2 ''-terpyridine ligand (Rtpy(center dot))(-) functionalized at the 4'-position (R = (CH3)(3)SiCH2, C6H5) catalyze mild and chemoselective hydroboration and hydrosilylation of functionalized ketones, aldehydes, imines, esters, and carboxamides with turnover numbers (TONs) of up to similar to 1000 and turnover frequencies (TOFs) of up to similar to 500 h(-1).Computational evaluation of the precatalyst synthesis and activation has revealed underappreciated complexity associated with the redox-active tpy chelate.