Stabilization of the Dinitrogen Analogue, Phosphorus Nitride.

Autor: Martinez JL; Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, United States., Lutz SA; Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, United States., Beagan DM; Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, United States., Gao X; Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, United States., Pink M; Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, United States., Chen CH; Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, United States., Carta V; Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, United States., Moënne-Loccoz P; Department of Chemical Physiology and Biochemistry, School of Medicine, Oregon Health & Science University, Portland, Oregon 97239, United States., Smith JM; Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, United States.
Jazyk: angličtina
Zdroj: ACS central science [ACS Cent Sci] 2020 Sep 23; Vol. 6 (9), pp. 1572-1577. Date of Electronic Publication: 2020 Sep 01.
DOI: 10.1021/acscentsci.0c00944
Abstrakt: The N 2 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 [(N 3 N)Mo-PN] - , N 3 N = [(Me 3 SiNCH 2 CH 2 ) 3 N] 3- ), which undergoes light-induced linkage isomerization to provide [(N 3 N)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.
Competing Interests: The authors declare no competing financial interest.
(Copyright © 2020 American Chemical Society.)
Databáze: MEDLINE
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