Valliant-Saunders, Karine published the artcileOxidation of Tertiary Silanes by Osmium Tetroxide, Product Details of C9H22OSi, the publication is Inorganic Chemistry (2007), 46(13), 5212-5219, database is CAplus and MEDLINE.
In the presence of an excess of pyridine ligand L, osmium tetroxide oxidizes tertiary silanes (Et3SiH, iPr3SiH, Ph3SiH, or PhMe2SiH) to the corresponding silanols. With L = 4-tert-butylpyridine (tBupy), OsO4(tBupy) oxidizes Et3SiH and PhMe2SiH to yield 100 ± 2% of silanol and the structurally characterized osmium(VI) μ-oxo dimer [OsO2(tBupy)2]2(μ-O)2 (1a). With L = pyridine (py), only 40-60% yields of R3SiOH are obtained, apparently because of coprecipitation of osmium(VIII) with [Os(O)2py2]2(μ-O)2 (1b). Excess silane in these reactions causes further reduction of the OsVI products, and similar osmium “over-reduction” is observed with PhSiH3, Bu3SnH, and boranes. The pathway for OsO4(L) + R3SiH involves an intermediate, which forms rapidly at 200 K and decays more slowly to products. NMR and IR spectra indicate that the intermediate is a monomeric OsVI-hydroxo-siloxo complex, trans-cis-cis-Os(O)2L2(OH)(OSiR3). Mechanistic studies and d. functional theory calculations indicate that the intermediate is formed by the [3 + 2] addition of an Si-H bond across an O:Os:O fragment. This is the first direct observation of a [3 + 2] intermediate in a σ-bond oxidation, though such species have previously been implicated in reactions of H-H and C-H bonds with OsO4(L) and RuO4.
Inorganic Chemistry published new progress about 17877-23-5. 17877-23-5 belongs to alcohols-buliding-blocks, auxiliary class Protection and Derivatization Reagent, name is Triisopropylsilanol, and the molecular formula is C4H10O2, Product Details of C9H22OSi.
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