The mechanism of the formation of silyl enol ethers from hydrosilanes and organic carbonyl compounds in the presence of cobalt carbonyls. Kinetic investigation of some reaction steps

István Kovács, Attila Sisak, F. Ungváry, László Markó

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

The cleavage of isobutyrylcobalt tetracarbonyl with triethylsilane gives (triethylsilyl)cobalt tetracarbonyl, isobutyraldehyde, dicobalt octacarbonyl, and the corresponding unsaturated and saturated silyl ethers. Silyl enol ether was also formed, along with order products, in the reaction of (trimethylsilyl) cobalt tetracarbonyl with isobutyraldehyde. The kinetics of both reactions were studied. The first one proceeds through an acylcobalt tricarbonyl intermediate that oxidatively adds hydrosilane in the rate-determining step and then gives the products in fast consecutive steps. The second reaction involves probably an (α-(trimethylsiloxy)isobutyl)cobalt tetracarbonyl intermediate formed from silylcobalt tetracarbonyl and aldehyde. Silyl enol ethers as main products will be provided by β-hydrogen elimination from α-siloxyalkyl complexes in both reactions.

Original languageEnglish
Pages (from-to)1025-1028
Number of pages4
JournalOrganometallics
Volume7
Issue number5
Publication statusPublished - 1988

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Carbonyl compounds
carbonyl compounds
Ethers
Cobalt
ethers
cobalt
Kinetics
kinetics
products
Aldehydes
Ether
Hydrogen
aldehydes
cleavage
elimination
hydrogen
isobutyraldehyde

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

The mechanism of the formation of silyl enol ethers from hydrosilanes and organic carbonyl compounds in the presence of cobalt carbonyls. Kinetic investigation of some reaction steps. / Kovács, István; Sisak, Attila; Ungváry, F.; Markó, László.

In: Organometallics, Vol. 7, No. 5, 1988, p. 1025-1028.

Research output: Contribution to journalArticle

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AU - Sisak, Attila

AU - Ungváry, F.

AU - Markó, László

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N2 - The cleavage of isobutyrylcobalt tetracarbonyl with triethylsilane gives (triethylsilyl)cobalt tetracarbonyl, isobutyraldehyde, dicobalt octacarbonyl, and the corresponding unsaturated and saturated silyl ethers. Silyl enol ether was also formed, along with order products, in the reaction of (trimethylsilyl) cobalt tetracarbonyl with isobutyraldehyde. The kinetics of both reactions were studied. The first one proceeds through an acylcobalt tricarbonyl intermediate that oxidatively adds hydrosilane in the rate-determining step and then gives the products in fast consecutive steps. The second reaction involves probably an (α-(trimethylsiloxy)isobutyl)cobalt tetracarbonyl intermediate formed from silylcobalt tetracarbonyl and aldehyde. Silyl enol ethers as main products will be provided by β-hydrogen elimination from α-siloxyalkyl complexes in both reactions.

AB - The cleavage of isobutyrylcobalt tetracarbonyl with triethylsilane gives (triethylsilyl)cobalt tetracarbonyl, isobutyraldehyde, dicobalt octacarbonyl, and the corresponding unsaturated and saturated silyl ethers. Silyl enol ether was also formed, along with order products, in the reaction of (trimethylsilyl) cobalt tetracarbonyl with isobutyraldehyde. The kinetics of both reactions were studied. The first one proceeds through an acylcobalt tricarbonyl intermediate that oxidatively adds hydrosilane in the rate-determining step and then gives the products in fast consecutive steps. The second reaction involves probably an (α-(trimethylsiloxy)isobutyl)cobalt tetracarbonyl intermediate formed from silylcobalt tetracarbonyl and aldehyde. Silyl enol ethers as main products will be provided by β-hydrogen elimination from α-siloxyalkyl complexes in both reactions.

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