Metal carbonyl-hydrosilane reactions and hydrosilation catalysis. Final report for period May 1, 1995 - August 14, 1999

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Manganese carbonyl complexes serve as hydrosilation precatalysts for selectively transforming a carbonyl group into a doxy methylene or a fully reduced methylene group. Substrates of interest include (1) aldehydes, ketones, carboxylic acids, silyl esters, and esters, and (2) their organometallic acyl counterparts. Two types of manganese precatalysts have been reported: (a) alkyl and acyl complexes (L)(CO){sub 4}MnR [L = CO, PPh{sub 3}; R = COCH{sub 3}, COPh, CH{sub 3}] and (b) halides (CO){sub 5}MnX and [(CO){sub 4}MnX]{sub 2} (X = Br, I). The former promote hydrosilation and deoxygenation catalysis; the latter promote dehydrogenative silation of alcohols and carboxylic acids as ... continued below

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27 p.

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Cutler, Alan R. April 14, 2001.

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Description

Manganese carbonyl complexes serve as hydrosilation precatalysts for selectively transforming a carbonyl group into a doxy methylene or a fully reduced methylene group. Substrates of interest include (1) aldehydes, ketones, carboxylic acids, silyl esters, and esters, and (2) their organometallic acyl counterparts. Two types of manganese precatalysts have been reported: (a) alkyl and acyl complexes (L)(CO){sub 4}MnR [L = CO, PPh{sub 3}; R = COCH{sub 3}, COPh, CH{sub 3}] and (b) halides (CO){sub 5}MnX and [(CO){sub 4}MnX]{sub 2} (X = Br, I). The former promote hydrosilation and deoxygenation catalysis; the latter promote dehydrogenative silation of alcohols and carboxylic acids as well as hydrosilation and deoxygenation of some metallocarboxylic acid derivatives. In every case studied, these Mn precatalysts are far more reactive or selective than traditional Rh(l) precatalysts. The reaction chemistry of the above and other Mn alkyl complexes with hydrosilanes was studied in order to probe catalysis mechanism(s). Thus, Mn(CO){sub 5} methyl, benzyl, acetyl, and benzoyl (4 p-substituents) complexes reacted with hydrosilines by four different mechanisms, which were established. A noteworthy development was that the methyl and benzoyl complexes gave moderate yields of a new ({eta}{sup 2}-Si-H) silane adduct (CO){sub 4}Mn(SiMe{sub 2}Ph)(H-SiMe{sub 2}Ph), which is stable in the presence of excess silane. This silane adduct promotes all three catalytic reactions; its extraordinary activity and potential selectivity are under study.

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27 p.

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OSTI as DE00805815

Medium: P; Size: 27 pages

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  • Other Information: PBD: 14 Apr 2001

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  • Report No.: DOE/ER14542
  • Grant Number: FG02-95ER14542
  • DOI: 10.2172/805815 | External Link
  • Office of Scientific & Technical Information Report Number: 805815
  • Archival Resource Key: ark:/67531/metadc739989

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  • April 14, 2001

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  • Oct. 18, 2015, 6:40 p.m.

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  • March 26, 2018, 8:28 p.m.

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Cutler, Alan R. Metal carbonyl-hydrosilane reactions and hydrosilation catalysis. Final report for period May 1, 1995 - August 14, 1999, report, April 14, 2001; Troy, New York. (digital.library.unt.edu/ark:/67531/metadc739989/: accessed August 17, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.