No abstract

The reaction of a silane with ozone results in the quantitative conversion of the Si-H bond to the Si-OH moiety. The mechanism of this oxidation has been elucidated by examination of: (a) relative rate data, (b) substituent effects, (c) deuterium isotope effects, (d) low-temperature nmr, and (e) uv spectroscopy. The mechanism proposed involves fast, reversible complexation of ozone (acting as a nucleophile) with the silicon atom, rate-determining electrophilic attack of ozone on the hydridic hydrogen, and decomposition into a R3Si • • OH radical pair which recombines to produce the silanol. From the relative rate data and substituent effects, a Hammett-like value, 8 *, characteristic of substituents bound to silicon, is derived.

No abstract

The mass spectral cracking patterns of 29 organosilicon compounds (PhSiR, XCeRCRSiMes, XC6H4SiMe3) were investigated, They are similar to the analogous carbon compounds except (a) no cracking which would require a carbon-silicon double bond in either the ion or the neutral is observed, and (b) extensive rearrangements occur in the XCeH4SiMe3 series which result in the formation of CiR1 234• and SiX+ species. Anomalies also appear when a particularly stable ion (as from o-PhCeH4SiMe3) may be formed.

spectrum 45 (100) [HOCHCH3], 67 (10) [C5H7], 103 (11) (M -CIC2H4O], 138 (8) [M -C2H4O], 182 (parent ion, not seen, as is usual for secondary and tertiary alcohols). Anal. Caled for C7Hi2OC12: