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Highly Electron‐Deficient and Air‐Stable Conjugated Thienylboranes
Author(s) -
Yin Xiaodong,
Chen Jiawei,
Lalancette Roger A.,
Marder Todd B.,
Jäkle Frieder
Publication year - 2014
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.201403700
Subject(s) - conjugated system , electrophile , chemistry , electron acceptor , trifluoromethyl , thiophene , boron , decomposition , acceptor , lewis acids and bases , polar effect , photochemistry , medicinal chemistry , crystallography , organic chemistry , polymer , catalysis , alkyl , physics , condensed matter physics
Abstract Introduced herein is a series of conjugated thienylboranes, which are inert to air and moisture, and even resist acids and strong bases. X‐ray analyses reveal a coplanar arrangement of the thiophene rings, an arrangement which facilitates p–π conjugation through the boron atoms despite the presence of highly bulky 2,4,6‐tri‐ tert ‐butylphenyl (Mes*) or 2,4,6‐tris(trifluoromethyl)phenyl ( F Mes) groups. Short B⋅⋅⋅F contacts, which lead to a pseudotrigonal bipyramidal geometry in the F Mes species, have been further studied by DFT and AIM analysis. In contrast to the Mes* groups, the highly electron‐withdrawing F Mes groups do not diminish the Lewis acidity of boron toward F − anions. These compounds can be lithiated or iodinated under electrophilic conditions without decomposition, thus offering a promising route to larger conjugated structures with electron‐acceptor character.