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Kinetics and mechanism of hydroboration of oct-1-and-4-ene by dimeric dialkylboranes
Jaganyi, D. and Govender, J. R. Kinetics and mechanism of hydroboration of oct-1-and-4-ene by dimeric dialkylboranes Chemical Papers, Vol.61, No. 1, 2007, 55-60
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Document type:
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Článok z časopisu / Journal Article |
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Collection:
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Chemical papers
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| Author(s) |
Jaganyi, D.
Govender, J. R.
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| Title |
Kinetics and mechanism of hydroboration of oct-1-and-4-ene by dimeric dialkylboranes
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| Journal name |
Chemical Papers
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| Publication date |
2007
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| Year available |
2007
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| Volume number |
61
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| Issue number |
1
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| ISSN |
0366-6352
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| Start page |
55
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| End page |
60
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| Place of publication |
Poland
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| Publisher |
Versita
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| Collection year |
2007
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| Language |
english
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| Subject |
250000 Chemical Sciences
250300 Organic Chemistry
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| Abstract/Summary |
The kinetics and mechanism of hydroboration of oct-1-and-4-ene with a series of dimeric dialkylboranes was investigated. The kinetic results showed that the hydroboration of terminal olefins proceeds via a three-halves-order mechanism, first-order with respect to the olefin and one-half-order with respect to the dimer. Using dicyclohexylborane, diisopinocamphenylborane, and 3,6-dimethylborepane the observed rate constants for the hydroboration of oct-4-ene were approximately 6 times smaller than those for oct-1-ene. Supporting computations showed that both steric and electronic effects influence the rate of hydroboration of both internal and terminal olefins. A model computational study of the isomerization of oct-4-ene with di(prop-2-yl)borane showed that formation of the terminal hydroborated complex is thermodynamically favored over the internal complex.
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