Hyvl Jakub, Yoshida Wesley Y, Rheingold Arnold L, Hughes Russell P, Cain Matthew F
Department of Chemistry, University of Hawai'i at Mānoa, 2545 McCarthy Mall, Honolulu, HI, 96822, USA.
Department of Chemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA, 92093, USA.
Chemistry. 2016 Dec 5;22(49):17562-17565. doi: 10.1002/chem.201604415. Epub 2016 Oct 24.
The trapping of a phosphinidene (R-P) in an NCN pincer is presented. Stabilized phosphinidene 1 was characterized by P{ H}, H, and C{ H} NMR spectroscopy, exhibiting an averaged C symmetry in solution between -60 and 60 °C. In the solid state, the phosphinidene is coordinated by one adjacent N atom featuring a formal P-N bond (1.757(2) Å) to give a five-membered ring with some aromatic character, confirmed by DFT calculations (B3LYP-D3/6-311G**++) to be the ground-state structure. Equilibration of the two N ligands occurs rapidly in solution via a "bell-clapper"-type process through an associative symmetric transition state calculated to lie 4.0 kcal mol above the ground state.
