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Rapid Dihydrogen Cleavage by Persistent Nitroxide Radicals under Frustrated Lewis Pair Conditions
Author(s) -
Tao Xin,
Kehr Gerald,
Wang Xiaowu,
Daniliuc Constantin G.,
Grimme Stefan,
Erker Gerhard
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.201602058
Subject(s) - frustrated lewis pair , lewis acids and bases , radical , chemistry , hydrogen atom abstraction , hydrogen atom , photochemistry , cleavage (geology) , nitroxide mediated radical polymerization , hydrogen , boron , catalysis , organic chemistry , materials science , group (periodic table) , polymer , polymerization , radical polymerization , fracture (geology) , composite material
Persistent radicals undergo hydrogen atom abstraction reactions with a great variety of substrates, but not with dihydrogen. It has now been found that the TEMPO radical splits dihydrogen under mild conditions in the presence of the strong bulky B(C 6 F 5 ) 3 boron Lewis acid. The reaction is thought to proceed by a typical frustrated Lewis pair mechanism with the TEMPO radical acting as the active Lewis base. The reaction was analyzed by DFT, which indicates that no significant spin density on the hydrogen atoms is accumulated along the H 2 splitting reaction path.