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A Novel N,P,C Cage Complex Formed by Rearrangement of a Tricyclic Phosphirane Complex: On the Importance of Non‐covalent Interactions
Author(s) -
Nesterov Vitaly,
Espinosa Arturo,
Schnakenburg Gregor,
Streubel Rainer
Publication year - 2014
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.201305061
Subject(s) - intramolecular force , chemistry , tricyclic , covalent bond , substituent , cycloaddition , stereochemistry , computational chemistry , organic chemistry , catalysis
The reaction of Li/Cl P ‐CPh 3 phosphinidenoid tungsten(0) complex 2 with dimethylcyanamide afforded tricyclic phosphirane complex 4 , an unprecedented rearrangement of which led to the novel N,P,C cage complex 6 . On the basis of DFT calculations, formation and intramolecular [3+2] cycloaddition of the transient nitrilium phosphane ylide complex 3 to a phenyl ring of the triphenylmethyl substituent to give 4 is proposed. Furthermore, theoretical evidence for terminal N ‐amidinophosphinidene complex 7 , formed by [2+1] cycloelimination from 4 , is provided, and the role of the electronic structure and non‐covalent interactions of intermediate 7 discussed.