Platinum-Catalyzed Reduction of DMF by 1,1,3,3-Tetramethyldisiloxane, HMeSi2OSiMe2H: New Intermediates HSiMe2OSiMe2OCH2NMe2 and HSiMe<

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• 作者：Jorge L. Martinez ; Hemant K. Sharma ; Renzo Arias-Ugarte ; Keith H. Pannell
• 刊名：Organometallics
• 出版年：2014
• 出版时间：June 23, 2014
• 年：2014
• 卷：33
• 期：12
• 页码：2964-2967
• 全文大小：305K
• ISSN：1520-6041

文摘

The use of Karstedt鈥檚 catalyst to study the reduction of Me₂NCHO (DMF) by the popular 鈥渄ual SiH鈥?containing tetramethyldisiloxane, HMe₂SiOSiMe₂H (1), has revealed that the first step in the process involves an initial single hydrosilylation to form HSiMe₂OSiMe₂OCH₂NMe₂ (3). This intermediate is readily isolated and purified via distillation. In the continued presence of the catalyst, 3 transforms to the transient tetrasiloxane HMe₂SiOSiMe₂OSiMe₂OSiMe₂OCH₂NMe₂ (4), along with the formation of Me₃N. The tetrasiloxane 4 itself transforms to Me₃N and (Me₂SiO)_n (n = 4鈥?). Despite the demonstrated reactivity of 3, it can also be used to perform the expected metal-catalyzed hydrosilylation chemistry of the SiH group as well as reactions of the SiOCH₂NMe₂ functionality involving siloxane chain extension and is thus an important new reagent for siloxane chemistry.