Stanislav Grabovskiy - Kinetic and Product Studies of the Reaction of Triorganosilanes with Dimethyldioxirane

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      Publication Details (including relevant citation   information):

      Organometallics, 2002, 21 (17), pp 3506–3510
      DOI: 10.1021/om0200095


      The oxidation of a variety of triorganosilanes by   dimethyldioxirane afforded the corresponding silanols in   quantitative yield. The reactions are performed at room   temperature using acetone or CCl4 as the solvent.   Under similar conditions, (Me3Si)3SiH gave   silanol in 80−90% yield together with other identified products.   Rate constants for these reactions were measured by following the   disappearance of the dimethyldioxirane absorption at 335 nm.   Depending on the substituents at the SiH moiety, the reactivities   cover ca. 4 orders of magnitude (from 5.8 ×   10-3 M-1  s-1 for (Me3SiO)3SiH   at 25 °C to 14.5 M-1  s-1 for (Me3Si)3SiH   at 15 °C). Arrhenius parameters were determined for a few   representative substrates. The reaction mechanism in terms of a   concerted oxygen insertion vs radical path is discussed in some   detail.

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