title: Synthesis of organic (trimethylsilyl)chalcogenolate salts Cat[TMS-E] (E = S, Se, Te): the methylcarbonate anion as a desilylating agent.
abstract: A high-yield synthesis of the class of (trimethylsilyl)chalcogenolate organic salts [Cat][TMS-E] (E = S, Se, Te; Cat = BMPyr, DMPyr, NMe4, nBu3MeP) is presented. The title compounds have been prepared by the strictly aprotic reaction between the respective bis(trimethylsilyl)chalcogenide (TMS2E) and methylcarbonate ionic liquids (ILs). This constitutes a novel reaction behavior of methylcarbonate ILs, acting as a nucleophilic desilylating agent and a Lewis base instead of as a Brønsted base. Thus prepared silylchalcogenolate salts represent an activated form of the multifunctional TMS2E reactant series. Pyrrolidinium TMS-S salts have proven to be excellent precursors for the synthesis of pyrrolidinium hexasulfides. The scope of the desilylation reaction can be extended to other silyl-bearing synthons such as (trimethylsilyl)azide and (trimethylsilyl)cyanide.
authors.affiliation: Fachbereich Chemie and Materials Science Center, Philipps-Universität Marburg , Hans-Meerwein-Strasse 4, 35032 Marburg, Germany.
authors.forename: Lars H
authors.initials: LH
authors.lastname: Finger
authors.affiliation: Fachbereich Chemie and Materials Science Center, Philipps-Universität Marburg , Hans-Meerwein-Strasse 4, 35032 Marburg, Germany.
authors.forename: Benjamin
authors.initials: B
authors.lastname: Scheibe
authors.affiliation: Fachbereich Chemie and Materials Science Center, Philipps-Universität Marburg , Hans-Meerwein-Strasse 4, 35032 Marburg, Germany.
authors.forename: Jörg
authors.initials: J
authors.lastname: Sundermeyer