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Reversible α‐Hydrogen and α‐Alkyl Elimination in PC(sp 3 )P Pincer Complexes of Iridium
Author(s) -
Jonasson Klara J.,
Polukeev Alexey V.,
Marcos Rocío,
Ahlquist Mårten S. G.,
Wendt Ola F.
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201503593
Subject(s) - pincer movement , iridium , chemistry , carbene , agostic interaction , bond cleavage , cleavage (geology) , alkyl , reductive elimination , migratory insertion , hydrogen , medicinal chemistry , photochemistry , catalysis , materials science , organic chemistry , metal , fracture (geology) , composite material
Despite significant progress in recent years, the cleavage of unstrained C(sp 3 )C(sp 3 ) bonds remains challenging. A CC coupling and cleavage reaction in a PC(sp 3 )P iridium pincer complex is mechanistically studied; the reaction proceeds via the formation of a carbene intermediate and can be described as a competition between α‐hydrogen and α‐alkyl elimination; the latter process was observed experimentally and is an unusual way of C(sp 3 )C(sp 3 ) bond scission, which has previously not been studied in detail. Mechanistic details that are based upon kinetic studies, activation parameters, and DFT calculations are also discussed. A full characterization of a CC agostic intermediate is presented.