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A Masked Phosphinidene Trapped in a Fluxional NCN Pincer
Author(s) -
Hyvl Jakub,
Yoshida Wesley Y.,
Rheingold Arnold L.,
Hughes Russell P.,
Cain Matthew F.
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201604415
Subject(s) - pincer movement , phosphinidene , chemistry , philosophy , photochemistry , biochemistry , catalysis
Abstract The trapping of a phosphinidene (R‐P) in an NCN pincer is presented. Stabilized phosphinidene 1 was characterized by 31 P{ 1 H}, 1 H, and 13 C{ 1 H} NMR spectroscopy, exhibiting an averaged C 2 v 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 −1 above the ground state.