A Transient V III –Alkylidene Complex: Oxidation Chemistry Including the Activation of N 2 to Afford a Highly Porous Honeycomb‐Like Framework

Honeycomb architectures from N 2 sequestration! The V III –bis‐neopentyl complex [(PNP)V(CH 2 t Bu) 2 ] (PNP=N[4‐Me‐2‐(P i Pr 2 )C 6 H 3 ] 2 − ) is a synthon to terminal V V alkylidene complexes when treated with two‐electron oxidants such as N 2 CPh 2 , O 2− sources such as OPPh 3 and N 2 O, and sulfide sources like S 8 and SPPh 3 . The likely V III –alkylidene intermediate, [(PNP)VCH t Bu], can also activate N 2 to form a honeycomb‐like packing rearrangement along the N 2 unit (see picture).