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Title: Manganese carbonyl bromide-catalyzed alcoholysis of the monohydrosilane HSiMe[sub 2]Ph

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

Authors:
;  [1]
  1. (Rensselaer Polytechnic Inst., Troy, NY (United States))
Publication Date:
OSTI Identifier:
7267477
Resource Type:
Journal Article
Journal Name:
Organometallics; (United States)
Additional Journal Information:
Journal Volume: 13:3; Journal ID: ISSN 0276-7333
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; ALCOHOLS; CHEMICAL REACTIONS; MONITORING; MANGANESE COMPLEXES; NMR SPECTRA; ORGANIC SILICON COMPOUNDS; DECOMPOSITION; SYNTHESIS; ACETONE; ALLYL RADICALS; BROMIDES; BUTANOLS; CARBONYLS; CATALYSTS; CHEMICAL REACTION KINETICS; EXPERIMENTAL DATA; LIGANDS; METHYL RADICALS; PHENYL RADICALS; PROPARGYL RADICALS; SILANES; SOLVENTS; ALKYL RADICALS; ARYL RADICALS; BROMINE COMPOUNDS; COMPLEXES; DATA; HALIDES; HALOGEN COMPOUNDS; HYDRIDES; HYDROGEN COMPOUNDS; HYDROXY COMPOUNDS; INFORMATION; KETONES; KINETICS; NUMERICAL DATA; ORGANIC COMPOUNDS; RADICALS; REACTION KINETICS; SILICON COMPOUNDS; SPECTRA; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties; 360602 - Other Materials- Structure & Phase Studies

Citation Formats

Gregg, B.T., and Cutler, A.R.. Manganese carbonyl bromide-catalyzed alcoholysis of the monohydrosilane HSiMe[sub 2]Ph. United States: N. p., 1994. Web. doi:10.1021/om00015a043.
Gregg, B.T., & Cutler, A.R.. Manganese carbonyl bromide-catalyzed alcoholysis of the monohydrosilane HSiMe[sub 2]Ph. United States. doi:10.1021/om00015a043.
Gregg, B.T., and Cutler, A.R.. Tue . "Manganese carbonyl bromide-catalyzed alcoholysis of the monohydrosilane HSiMe[sub 2]Ph". United States. doi:10.1021/om00015a043.
@article{osti_7267477,
title = {Manganese carbonyl bromide-catalyzed alcoholysis of the monohydrosilane HSiMe[sub 2]Ph},
author = {Gregg, B.T. and Cutler, A.R.},
abstractNote = {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 solutions of 2-butanol and HSiMe[sub 2]-Ph with 1.4 mol% precatalyst [Mn(CO)[sub 4]Br][sub 2]. 29 refs., 5 tabs.},
doi = {10.1021/om00015a043},
journal = {Organometallics; (United States)},
issn = {0276-7333},
number = ,
volume = 13:3,
place = {United States},
year = {1994},
month = {3}
}