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Creators/Authors contains: "Rahman, Md. Mamdudur"

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  1. ; ; ; ; ; (, Organic & Biomolecular Chemistry)
    The mechanism of the asymmetric silylation of alcohols with isothiourea catalysts was studied by employing reaction progress kinetic analysis. These reactions were developed by the Wiskur group, and use triphenyl silyl chloride and chiral isothiourea catalysts to silylate the alcohols. While the order of most reaction components was as expected (catalyst, amine base, alcohol), the silyl chloride was determined to be a higher order. This suggested a multistep mechanism between the catalyst and silyl chloride, with the second equivalent of silyl chloride assisting in the formation of the reactive intermediate leading to the rate-determining step. Through the addition of additives and investigating changes in the silyl chloride, an understanding of the catalyst equilibrium emerged for this reaction and provided pathways for further reaction development. 
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  2. ; ; ; ; (, Chemical Science)
    null (Ed.)
    Carbon atom functionalization via generation of carbanions is the cornerstone of carborane chemistry. In this work, we report the synthesis and structural characterization of free ortho-carboranyl [C2B10H11]−, a three-dimensional inorganic analog of the elusive phenyl anion that features a “naked” carbanion center. The first example of a stable, discrete C(H)-deprotonated carborane anion was isolated as a completely separated ion pair with a crown ether-encapsulated potassium cation. An analogous approach led to the isolation and structural characterization of a doubly deprotonated 1,1′-bis(o-carborane) anion [C2B10H10]22−, which is the first example of a discrete molecular dicarbanion. These reactive carbanions are key intermediates in carbon vertex chemistry of carborane clusters. 
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  3. ; ; (, Organometallics)
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