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Intramolecular HAr Ligand Exchange between Silicon and Boron: Functionality Transfer of SiH to BH
Author(s) -
Kawachi Atsushi,
Morisaki Hiroshi,
Nishioka Norimasa,
Yamamoto Yohsuke
Publication year - 2012
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201100678
Subject(s) - tetracoordinate , moiety , ligand (biochemistry) , chemistry , intramolecular force , hydride , boron , benzaldehyde , silicon , medicinal chemistry , silylation , stereochemistry , crystallography , photochemistry , catalysis , organic chemistry , metal , biochemistry , computer graphics (images) , receptor , computer science , planar
o ‐C 6 H 4 (SiR 3 − n H n )(BMes 2 ) ( 1 ; R=Me, Ph; n =1, 2) undergo MesH (Mes=mesityl) ligand exchange between the silicon atom and the boron atom to form o ‐C 6 H 4 (SiMesR 3 − n H n − 1 )(BMesH) ( 6 ) upon heating. The resulting hydroborane intermediates ( 6 ) immediately react with benzaldehyde to afford their corresponding benzyloxyboranes ( 5 ). A DFT study of model compounds reveals the transition states of the ligand exchange. A hydride abstraction from the silicon atom by the boron center is key to reaching the transition states, which include the tricoordinate silyl‐cation moiety and the tetracoordinate hydridoborate moiety.