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Stabilization of the Dinitrogen Analogue, Phosphorus Nitride

2020; American Chemical Society; Volume: 6; Issue: 9 Linguagem: Inglês

10.1021/acscentsci.0c00944

2374-7951

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

Magnetism in coordination complexes

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 C≡N t Bu 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.