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The chemistry of vanadium has seen remarkable activity in the past 50 years. In the present review, reactions catalyzed by homogeneous and supported vanadium complexes from 2008 to 2018 are summarized and discussed. Particular attention is given to mechanistic and kinetics studies of vanadium-catalyzed reactions including oxidations of alkanes, alkenes, arenes, alcohols, aldehydes, ketones, and sulfur species, as well as oxidative C–C and C–O bond cleavage, carbon–carbon bond formation, deoxydehydration, haloperoxidase, cyanation, hydrogenation, dehydrogenation, ring-opening metathesis polymerization, and oxo/imido heterometathesis. Additionally, insights into heterogeneous vanadium catalysis are provided when parallels can be drawn from the homogeneous literature.

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Reaction of 2 or 3 equiv of potassium 1,3-bis(trimethylsilyl) with the triflate salts of Ce, Nd, Eu, Tb, and Yb gives the corresponding neutral bis-(Yb, Eu) and tris-(Ce, Nd, Tb) allyl lanthanide complexes in yields ranging from 40 to 80%. These complexes, which have been crystallographically characterized, initiate the polymerization of methyl methacrylate (MMA), but with poor turnover frequencies when compared with the corresponding salt complexes of the type K[LnA′ 3 ]. K[A′] itself initiates MMA polymerization, however, and its presence as an ion-pair in the salt complexes may contribute to the activity of heterometallic lanthanide catalysts.