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Stimuli‐Responsive Frustrated Lewis‐Pair‐Type Reactivity of a Tungsten Iminoazaphosphiridine Complex
Author(s) -
Villalba Franco José Manuel,
Schnakenburg Gregor,
Sasamori Takahiro,
Espinosa Ferao Arturo,
Streubel Rainer
Publication year - 2015
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.201501628
Subject(s) - frustrated lewis pair , reactivity (psychology) , tungsten , type (biology) , materials science , psychology , chemistry , geology , lewis acids and bases , medicine , catalysis , metallurgy , paleontology , biochemistry , alternative medicine , pathology
Reactions of 3‐imino‐azaphosphiridine complexes 1 a,b with carbodiimides 2 a,b , isocyanates 3 a,b , and carbon dioxide are described. Whereas exchange of the carbodiimide unit occurs in the first case, an overall ring expansion takes place with phenyl isocyanate ( 3 a ) and carbon dioxide to yield complexes 4 and 5 bearing novel 1,3,5‐oxazaphospholane ligands; the isopropyl derivative 3 b did not react under these conditions. DFT calculations provide insight into the pathway of the reaction with carbon dioxide with model complex 1 c , revealing effects of initial non‐covalent interactions with the substrate onto the ring bonding, thus triggering an initially masked frustrated Lewis‐pair‐type behavior.