Premium
From a Stable Silanone Complex to Isolable, Donor‐Supported Silicoxonium Halides [LSi(dmap)OSiMe 3 ] + X −
Author(s) -
Xiong Yun,
Yao Shenglai,
Irran Elisabeth,
Driess Matthias
Publication year - 2011
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.201101610
Subject(s) - chemistry , iodide , halide , bromide , trimethylsilyl , methyl iodide , ligand (biochemistry) , medicinal chemistry , nuclear magnetic resonance spectroscopy , ionic bonding , stereochemistry , organic chemistry , ion , biochemistry , receptor
The first donor‐stabilized silylated silicoxonium species [ L SiOSiMe 3 ] + ( L =(RN)C(CH 2 )CHCMe(NR), R=2,6‐ i Pr 2 C 6 H 3 ) have been synthesized from the reaction of the dmap‐supported (dmap= p ‐dimethylaminopyridine) silanone complex [ L Si(dmap)O] ( 1 ) with trimethylsilyl halides. Although the reaction with Me 3 SiCl leads directly to the SiO addition product [ L Si(Cl)OSiMe 3 ] ( 2 ), the ionic silicoxonium bromide [ L (dmap)SiOSiMe 3 ] + Br − ( 3 ) can be obtained as a primary product of the reaction with Me 3 SiBr, which affords [ L Si(Br)OSiMe 3 ] ( 4 ) with release of the dmap ligand at room temperature in THF. In the case of Me 3 SiI, the reaction furnishes the silicoxonium iodide [ L (dmap)SiOSiMe 3 ] + I − ( 5 ) as the most stable species. Compounds 2 – 5 were isolated and fully characterized through multinuclear NMR spectroscopy, mass spectrometry, elemental analyses, and single‐crystal X‐ray diffraction analyses.