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Competition for Hydride Between Silicon and Boron: Synthesis and Characterization of a Hydroborane‐Stabilized Silylium Ion
Author(s) -
Gao Haopeng,
Müller Robert,
Irran Elisabeth,
Klare Hendrik F. T.,
Kaupp Martin,
Oestreich Martin
Publication year - 2022
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.202104464
Subject(s) - hydride , chemistry , boron , silicon , ion , lewis acids and bases , cationic polymerization , characterization (materials science) , crystallography , hydrogen , inorganic chemistry , polymer chemistry , nanotechnology , organic chemistry , materials science , catalysis
Potent main‐group Lewis acids are capable of activating element‐hydrogen bonds. To probe the rivalry for hydride between silylium‐ and borenium‐ion centers, a neutral precursor with the hydrosilane and hydroborane units in close proximity on a naphthalene‐1,8‐diyl platform was designed. Abstraction of one hydride leads to a hydroborane‐stabilized silylium ion rather than a hydrosilane‐coordinated borenium ion paired with [B(C 6 F 5 ) 4 ] − or [HCB 11 Cl 11 ] − as counteranions. Characterization by multinuclear NMR spectroscopy and X‐ray diffraction supported by DFT calculations reveals a cationic, unsymmetrical open three‐center, two‐electron (3c2e) Si−H−B linkage.