title: Platinum-Catalyzed Reduction of DMF by 1,1,3,3-Tetramethyldisiloxane, HMeSi2OSiMe2H: New Intermediates HSiMe2OSiMe2OCH2NMe2and HSiMe2(OSiMe2)3OCH2NMe2and Their Further Chemical Reactivity.
abstract: 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,3transforms to the transient tetrasiloxane HMe2SiOSiMe2OSiMe2OSiMe2OCH2NMe2(4), along with the formation of Me3N. The tetrasiloxane4itself transforms to Me3N and (Me2SiO)n(n= 4-6). Despite the demonstrated reactivity of3, it can also be used to perform the expected metal-catalyzed hydrosilylation chemistry of the SiH group as well as reactions of the SiOCH2NMe2functionality involving siloxane chain extension and is thus an important new reagent for siloxane chemistry.
authors.affiliation: Department of Chemistry, The University of Texas at El Paso , El Paso, Texas 79968-0513, United States.
authors.forename: Jorge L
authors.initials: JL
authors.lastname: Martinez
authors.affiliation: Department of Chemistry, The University of Texas at El Paso , El Paso, Texas 79968-0513, United States.
authors.forename: Hemant K
authors.initials: HK
authors.lastname: Sharma
authors.affiliation: Department of Chemistry, The University of Texas at El Paso , El Paso, Texas 79968-0513, United States.
authors.forename: Renzo
authors.initials: R
authors.lastname: Arias-Ugarte
authors.affiliation: Department of Chemistry, The University of Texas at El Paso , El Paso, Texas 79968-0513, United States.
authors.forename: Keith H
authors.initials: KH
authors.lastname: Pannell