TY - JOUR
T1 - A Potassium Diboryllithate
T2 - Synthesis, Bonding Properties, and the Deprotonation of Benzene
AU - Ohsato, Takuto
AU - Okuno, Yuri
AU - Ishida, Shintaro
AU - Iwamoto, Takeaki
AU - Lee, Ka Ho
AU - Lin, Zhenyang
AU - Yamashita, Makoto
AU - Nozaki, Kyoko
N1 - Funding Information:
This research was supported by Grants-in-Aid for Scientific Research on Innovative Areas [“Stimuli-responsive Chemical Species for Creation of Functional Molecules” (No. 2408), JSPS KAKENHI Grant Numbers JP24109012 (M.Y.) and JP24109004 (T.I.)]; “Precise Formation of a Catalyst Having a Specified Field for Use in Extremely Difficult Substrate Conversion Reactions”, 15H05796 (K.N.)] from MEXT and JSPS, Grants-in-Aid for Scientific Research (B) [26288019 (M.Y.)] from MEXT, HKUST603313 (Z.L.) and CUHK7/CRF/12G (Z.L.) from the Research Grants Council of Hong Kong, CREST (14529307, M.Y.) from JST, and research grants from The Science Research Promotion Fund (M.Y.) and The Asahi Glass Foundation (M.Y.). We thank Prof. Tamejiro Hiyama (Chuo University) for providing access to an X-ray diffractometer. Parts of the theoretical calculations were carried out using resources at the Research Center for Computational Science, Okazaki, Japan.
Publisher Copyright:
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2016/9/12
Y1 - 2016/9/12
N2 - A potassium diboryllithate (B2LiK) was synthesized and structurally characterized. DFT calculations, including NPA and AIM analyses of B2LiK, revealed ionic interactions between the two bridging boryl anions and Li+and K+. Upon standing in benzene, B2LiK deprotonated the solvent to form a hydroborane and a phenylborane. On the basis of DFT calculations, a detailed reaction mechanism, involving deprotonation and hydride/phenyl exchange processes, is proposed. An NBO analysis of the transition state for the deprotonation of benzene suggests that the deprotonation should be induced by the coordination of benzene to the K+.
AB - A potassium diboryllithate (B2LiK) was synthesized and structurally characterized. DFT calculations, including NPA and AIM analyses of B2LiK, revealed ionic interactions between the two bridging boryl anions and Li+and K+. Upon standing in benzene, B2LiK deprotonated the solvent to form a hydroborane and a phenylborane. On the basis of DFT calculations, a detailed reaction mechanism, involving deprotonation and hydride/phenyl exchange processes, is proposed. An NBO analysis of the transition state for the deprotonation of benzene suggests that the deprotonation should be induced by the coordination of benzene to the K+.
KW - benzene
KW - boron
KW - computational chemistry
KW - structure determination
KW - superbases
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U2 - 10.1002/anie.201605005
DO - 10.1002/anie.201605005
M3 - Article
AN - SCOPUS:84994410792
SN - 1433-7851
VL - 55
SP - 11426
EP - 11430
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 38
ER -