Ein aromatisches Diphosphatriazolat‐Anion durch formale anorganische “Klick”‐Chemie

The polarized, cationic diphosphene [(ClImDipp)P=P(Dipp)]+ as the triflate salt 7[OTf](ClImDipp=4,5‐dichloro‐1,3‐bis(Dipp)‐imidazol‐2‐yl; Dipp=2,6‐diisopropylphenyl) reacts with azides of type RN3 (R=Dipp or Dmp; Dmp=2,5‐dimethylphenyl) in a [2+3] cycloaddition reaction followed by the release of N2 and a subsequent electrocyclic ring‐closing reaction to azadiphosphiridine salts [(ClImDipp)P‐P(Dipp)‐N(R)]10a,b[OTf] (R=Dipp or Dmp). The reaction of 7[X] (X=OTf, GaCl4) with the electron‐rich azides Me3SiN3 and NaN3 give the unusual diphosphenimine derivatives [(ClImDipp)P−P(Dipp)=N(SiMe3)]+ (11[OTf]) and [(ClImDipp)P−P(Dipp)=N(GaCl3)] (12), respectively, featuring an acyclic P2N moiety. Theoretical calculations provide insights into the reaction mechanisms to the cyclic and acyclic forms, in which the thermodynamic stability of the latter prevents the electrocyclic ring closure.

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Isolation of Azadiphosphiridines and Diphosphenimines by Cycloaddition of Azides and a Cationic Diphosphene

Schwedtmann

Hennersdorf

Bauzá

et al. 2017

Angewandte Chemie

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Isolation of Azadiphosphiridines and Diphosphenimines by Cycloaddition of Azides and a Cationic Diphosphene

et al. 2017

View full text Add to dashboard Cite

The polarized, cationic diphosphene [( Im )P=P(Dipp)] as the triflate salt 7[OTf]( Im =4,5-dichloro-1,3-bis(Dipp)-imidazol-2-yl; Dipp=2,6-diisopropylphenyl) reacts with azides of type RN (R=Dipp or Dmp; Dmp=2,5-dimethylphenyl) in a [2+3] cycloaddition reaction followed by the release of N and a subsequent electrocyclic ring-closing reaction to azadiphosphiridine salts [( Im )P-P(Dipp)-N(R)]10a,b[OTf] (R=Dipp or Dmp). The reaction of 7[X] (X=OTf, GaCl ) with the electron-rich azides Me SiN and NaN give the unusual diphosphenimine derivatives [( Im )P-P(Dipp)=N(SiMe )] (11[OTf]) and [( Im )P-P(Dipp)=N(GaCl )] (12), respectively, featuring an acyclic P N moiety. Theoretical calculations provide insights into the reaction mechanisms to the cyclic and acyclic forms, in which the thermodynamic stability of the latter prevents the electrocyclic ring closure.

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Ein aromatisches Diphosphatriazolat‐Anion durch formale anorganische “Klick”‐Chemie

Abstract: High Five: Eine formale Cycloadditionsreaktion zwischen einer P2‐Quelle und Azid (N3)− führt zum neuartigen [P2N3]−‐Anion. Experimentelle und computergestützte Studien bestätigen einen erheblichen aromatischen Charakter dieses faszinierenden anorganischen Bausteins.

Cited by 2 publications

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Isolation of Azadiphosphiridines and Diphosphenimines by Cycloaddition of Azides and a Cationic Diphosphene

Isolation of Azadiphosphiridines and Diphosphenimines by Cycloaddition of Azides and a Cationic Diphosphene

Isolation of Azadiphosphiridines and Diphosphenimines by Cycloaddition of Azides and a Cationic Diphosphene

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