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Crystalline BP‐Doped Phenanthryne via Photolysis of The Elusive Boraphosphaketene
Author(s) -
Yang Wenlong,
Krantz Kelsie E.,
Dickie Diane A.,
Molino Andrew,
Wilson David J. D.,
Gilliard Robert J.
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201916362
Subject(s) - decarbonylation , chemistry , carbene , reactivity (psychology) , phosphide , photodissociation , medicinal chemistry , ligand (biochemistry) , alkyl , photochemistry , stereochemistry , organic chemistry , metal , catalysis , medicine , biochemistry , alternative medicine , receptor , pathology
The synthesis and reactivity study of the first isolable boraphosphaketene, cyclic(alkyl)(amino) carbene (CAAC)‐borafluorene‐P=C=O ( 2 ), is described. Photolysis of compound 2 results in the formation of CAAC‐stabilized BP‐doped phenanthryne ( 3 ) through tandem decarbonylation, monoatomic phosphide insertion, and ring‐expansion. Notably, while BN‐doped phenanthryne was previously discussed as a reactive intermediate which could not be isolated, the heavier BP‐doped analogue exhibits remarkable solution and solid‐state stability. The reactivity of 2 with stable carbenes was also explored. Addition of CAAC to 2 led to migration of the original CAAC ligand from boron to phosphorus and coordination of the added CAAC to carbon, affording compound 4 . Reaction of 1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene (NHC) with 2 resulted in N−C bond activation to give the unusual spiro‐heterocyclic compound ( 5 ).