Bis(η⁵:η¹-pentafulvene)niobium(V) complexes. Efficient synthons for niobium carbene and imido derivatives

Transition-metal carbene complexes and their reactivities are a key topic of chemistry. They are an integral part of researches in catalysis, organic synthesis, coordination chemistry, and numerous other areas. In this context, we report the synthesis of a low-valent bis(η⁵:η¹-(di-p-tolyl)-pentafulvene)niobium chloride. Owing to the π-η⁵:σ-η¹ coordination mode of the pentafulvenes and the resulting high nucleophilic character of the exocyclic carbon atom of the ligand, the bis(η⁵:η¹-pentafulvene)niobium complex is able to achieve the umpolung of a coordinated vinyl unit and the resulting formation of the first η⁵:η¹ cyclic niobium Schrock carbene complex. This new synthetic route is, in comparison to classical α-hydrogen elimination reactions or thermolysis of diazo compounds, completely unprecedented. The reactivity of the cyclic carbene function and the remaining fulvene ligand is demonstrated by double N-H bond activation of primary amines to niobium imido complexes. (copyright 2018 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)