Platinum-Catalyzed Reduction of DMF by 1,1,3,3-Tetramethyldisiloxane, HMeSi<sub>2</sub>OSiMe<sub>2</sub>H: New Intermediates HSiMe<sub>2</sub>OSiMe<sub>2</sub>OCH<sub>2</sub>NMe<sub>2</sub> and HSiMe<sub>2</sub>(OSiMe<sub>2</sub>)<sub>3</sub>OCH<sub>2</sub>NMe<sub>2</sub> and Their Further Chemical Reactivity
作者:Jorge L. Martinez、Hemant K. Sharma、Renzo Arias-Ugarte、Keith H. Pannell
DOI:10.1021/om500439p
日期:2014.6.23
The use of Karstedt's catalyst to study the reduction of Me2NCHO (DMF) by the popular "dual SiH"-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 = 4-6). 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.
(Me<sub>3</sub>N)Mo(CO)<sub>5</sub>-Catalyzed Reduction of DMF by Disiloxane and Disilane Moieties: Fate of the Silicon-Containing Fragments
作者:Hemant K. Sharma、Renzo Arias-Ugarte、David Tomlinson、Rie Gappa、Alejandro J. Metta-Magaña、Haruhiko Ito、Keith H. Pannell
DOI:10.1021/om301206c
日期:2013.7.22
hydrodisilanes, R3SiSiMe2H (2; R = alkyl, aryl), as reductants for N,N-dimethylformamide (DMF) in the presence of (Me3N)Mo(CO)5 as a catalyst led to the formation of a series of novel and structurally interesting siloxanes as well as trimethylamine. In the case of 1 the cyclic poly(dimethylsiloxanes) D4 and D6 are obtained, and for 2 the products are bis(disilyl) ethers, (R3SiSiMe2)2O. Siloxymethylamine