The rhenium(V)-nitride complex (PNP)Re(N)(Cl) (PNP = N(CH2CH2PtBu2)2) is distinctive because the nitride ligand can be derived from atmospheric N2 and can potentially undergo further reactions. Achieving this goal requires an understanding of the balance between reactivity at the metal center, the supporting ligand, and the nitride ligand. This presentation will explore the oxidative chemistry of (PNP)Re(N)(Cl), which has yielded products resulting from rhenium and supporting ligand oxidation, including formation of complexes where the central amide in the pincer ligand is oxidized to a nitroxide. A series of rhenium(V)- and rhenium(VI)-nitride complexes have been characterized, allowing us to compare effects of oxidation of the metal center and chemical oxidation of the supporting pincer ligand. The efficacy of PCET reactions with (PNP)Re(N)(Cl) will also be discussed, both as a means to reductively functionalize the nitride ligand and oxidatively form it. The conclusions drawn from these studies contribute to the design of new systems that can achieve both the reductive cleavage of N2 and subsequent functionalization of the nitride ligand.

Oxidative reactivity of a rhenium nitride complex

255th National Meeting (2018)

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