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Nitrogen‐Based Lewis Acids Derived from Phosphonium Diazo Cations
Author(s) -
Waked Alexander E.,
Ostadsharif Memar Rouzbeh,
Stephan Douglas W.
Publication year - 2018
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.201804183
Subject(s) - chemistry , medicinal chemistry , diazo , lewis acids and bases , phosphonium , cleavage (geology) , stereochemistry , nitrogen , catalysis , polymer chemistry , organic chemistry , geotechnical engineering , fracture (geology) , engineering
Reaction of PPh 3 and [( p ‐ClC 6 H 4 )N 2 ][BF 4 ] affords [( p ‐ClC 6 H 4 )N(PPh 3 )N(PPh 3 )][BF 4 ] 1 , while reaction with (Ph 2 PCH 2 ) 2 gave [( p ‐ClC 6 H 4 )(NPh 2 PCH 2 ) 2 )][BF 4 ] 2 . These species confirm the Lewis acidity of [( p ‐ClC 6 H 4 )N 2 (PR 3 )][BF 4 ] cations at N. In contrast, use of bulky phosphines afford the species [ArN 2 (PR 3 )][BF 4 ] (R= t Bu 3 , Mes 4 ). Compound 3 undergoes one electron reduction to give the stable radical [( p ‐ClC 6 H 4 )N 2 (P t Bu 3 )] . 5 . Combination of 3 and P t Bu 3 acts as an FLP to effect (SPh) 2 cleavage, generating [PhSP t Bu 3 ] + and the radical [ArN 2 (PR 3 )] . . Collectively, these data affirm the ability of the cations [ArN 2 (PR 3 )] + to behave as one or two electron acceptors.