A Transient V^III–Alkylidene Complex: Oxidation Chemistry Including the Activation of N₂ to Afford a Highly Porous Honeycomb‐Like Framework

Abstract

Honeycomb architectures from N2 sequestration! The VIII–bis-neopentyl complex [(PNP)V(CH2tBu)2] (PNP=N[4-Me-2-(PiPr2)C6H3]2−) is a synthon to terminal VV alkylidene complexes when treated with two-electron oxidants such as N2CPh2, O2− sources such as OPPh3 and N2O, and sulfide sources like S8 and SPPh3. The likely VIII–alkylidene intermediate, [(PNP)VCHtBu], can also activate N2 to form a honeycomb-like packing rearrangement along the N2 unit (see picture).