Stabilization of the Dinitrogen Analogue, Phosphorus Nitride

Jorge L. Martinez, Sean A. Lutz, Daniel M. Beagan, Xinfeng Gao, Maren Pink, Chun Hsing Chen, Veronica Carta, Pierre Moënne-Loccoz, Jeremy M. Smith

Research output: Contribution to journalArticlepeer-review

16 Scopus citations


The N2 analogue phosphorus nitride (PN) was the first phosphorus-containing compound to be detected in the interstellar medium; however, this thermodynamically unstable compound has a fleeting existence on Earth. Here, we show that reductive coupling of iron(IV) nitride and molybdenum(VI) phosphide complexes assembles PN as a bridging ligand in a structurally characterized bimetallic complex. Reaction with CNtBu releases the mononuclear complex [(N3N)Mo - PN]-, N3N = [(Me3SiNCH2CH2)3N]3-), which undergoes light-induced linkage isomerization to provide [(N3N)Mo - NP]-, as revealed by photocrystallography. While structural and spectroscopic characterization, supported by electronic structure calculations, reveals the PN multiple bond character, coordination to molybdenum induces a nucleophilic character at the terminal atom of the PN/NP ligands. Indeed, the linkage isomers can be trapped in solution by reaction with a Rh(I) electrophile.

Original languageEnglish (US)
Pages (from-to)1572-1577
Number of pages6
JournalACS Central Science
Issue number9
StatePublished - Sep 23 2020

ASJC Scopus subject areas

  • General Chemistry
  • General Chemical Engineering


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