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- W2951371503 abstract "The dimeric manganese carbonyl bromide [Mn(CO)[sub 4]Br][sub 2] is an effective catalyst for the alcoholysis of dimethylphenylsilane in benzene at room temperature. Preparative scale procedures using a 1200:1200:1 mixture of alcohol, HSiMe[sub 2]Ph, and [Mn(CO)[sub 4]Br][sub 2] (0.084 mol%) afforded samples of analytically pure alkoxysilanes in good yields. tert-Butyl alcohol, for example, gave (CH[sub 3])[sub 3]COSiMe[sub 2]Ph in 82% yield after a 35-min reaction time, and allyl and propargyl alcohols quantitatively transformed to their alkoxysilane derivatives, with no evidence of competing hydrosilation of the carbon-carbon multiple bonds. Competitive reactions involving 1:1:1 mixtures of 2-butanol-acetone-HSiMe[sub 2]Ph and [Mn(CO)[sub 4]Br][sub 2] as catalyst exhibited chemoselective alcoholysis of dimethyl-phenylsilane. [sup 1]H NMR spectral monitoring of catalyzed reactions between methanol or 2-butanol and HSiMe[sub 2]Ph was used in screening other manganese carbonyl complexes as potential HSiMe[sub 2]Ph alcoholysis catalysts. Their reaction times varied as follows: [Mn(CO)[sub 4]Br][sub 2] > Mn(CO)[sub 5]Br [much gt] Mn(CO)[sub 5]CH[sub 3] [approx] Mn(CO)[sub 5]C(O)Ph > Mn(PPh[sub 3])(CO)[sub 4]Br > Mn(PPh[sub 3])(CO)[sub 4]C(O)CH[sub 3] [much gt] Mn(CO)[sub 5](SiMe[sub 2]Ph) [much gt] Mn[sub 2](CO)[sub 10] [approx] Rh(PPh[sub 3])[sub 3]Cl (no reaction). Solvent-dependent turnover frequencies were determined for the [Mn(CO)[sub 4]Br][sub 2]-catalyzed dehydrocoupling of 2-butanol and HSiMe[sub 2]Ph for 0.289 M solutionsmore » of 2-butanol and HSiMe[sub 2]-Ph with 1.4 mol% precatalyst [Mn(CO)[sub 4]Br][sub 2]. 29 refs., 5 tabs.« less" @default.
- W2951371503 created "2019-06-27" @default.
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- W2951371503 date "2010-08-19" @default.
- W2951371503 modified "2023-09-26" @default.
- W2951371503 title "ChemInform Abstract: Manganese Carbonyl Bromide-Catalyzed Alcoholysis of the Monohydrosilane HSiMe2Ph." @default.
- W2951371503 cites W2072473343 @default.
- W2951371503 doi "https://doi.org/10.1002/chin.199430160" @default.
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