Reactivity of a stable phosphinonitrene towards small molecules.
The room-temperature stable phosphinonitrene 1 undergoes a thermal rearrangement into heterocycle 2 through a process involving a nitrene insertion into a CH bond. In the presence of acetonitrile, a nitrene-acetonitrile adduct has been isolated; then it first rearranges into a ketenimine and subsequently into a rare example of diazaphosphete. Compound 1 also splits water, carbon dioxide, carbon disulfide, and elemental sulfur, although it reacts with white phosphorus, leading to a P5 N cluster formally resulting from the insertion of the PN moiety into a P-P edge of the P4 tetrahedron.
UCSD-CNRS Joint Research Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, CA 92093-0343 (USA) http://bertrandgroup.ucsd.edu; Current address: Institut für Anorganische und Analytische Chemie Westfälische Wilhelms-Universität Münster, Corrensstrasse 30, 48149 Münster (Germany).
Fabian
F
Dielmann
Guy
G
Bertrand
carbenes; nitrenes; phosphorus; small-molecule activation; thiosulfinylamino group