A Transient VIII–Alkylidene Complex: Oxidation Chemistry Including the Activation of N2 to Afford a Highly Porous Honeycomb-Like Framework

Authors


  • We thank Indiana University-Bloomington, the Dreyfus Foundation, the Sloan Foundation, and the US NSF for financial support of this research. U.J.K. acknowledges Baxter Pharmaceutical Co. for financial support, and Dr. John Tomaszewski for aid in NMR spectroscopic measurements. Prof. Amar Flood and Edward Witlicki are thanked for help with Raman spectra.

Abstract

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Honeycomb architectures from N2sequestration! 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[DOUBLE BOND]CHtBu], can also activate N2 to form a honeycomb-like packing rearrangement along the N2 unit (see picture).

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