Stabilization of the Dinitrogen Analogue, Phosphorus Nitride
| Autor: | Veronica Carta, Sean A. Lutz, Pierre Moënne-Loccoz, Jorge L. Martinez, Chun-Hsing Chen, Maren Pink, Daniel M. Beagan, Jeremy M. Smith, Xinfeng Gao |
|---|---|
| Rok vydání: | 2020 |
| Předmět: |
010405 organic chemistry
Phosphide General Chemical Engineering chemistry.chemical_element Bridging ligand General Chemistry Nitride 010402 general chemistry 01 natural sciences 0104 chemical sciences Chemistry Crystallography chemistry.chemical_compound chemistry Nucleophile Molybdenum Electrophile Linkage isomerism QD1-999 Isomerization Research Article |
| Zdroj: | ACS Central Science ACS Central Science, Vol 6, Iss 9, Pp 1572-1577 (2020) |
| ISSN: | 2374-7951 2374-7943 |
| Popis: | 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≡NtBu 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. The highly reactive interstellar gas, phosphorus nitride, is assembled and stabilized as a reactive ligand in transition metal complexes. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|