Experimental and Theoretical Study of Oxygen Insertion into Trialkylsilanes by Methyltrioxorhenium Catalyst
dc.contributor.author | Tan, Haisong | |
dc.contributor.author | Yoshikawa, Akihiko | |
dc.contributor.author | Gordon, Mark | |
dc.contributor.author | Gordon, Mark | |
dc.contributor.author | Espenson, James | |
dc.contributor.department | Ames National Laboratory | |
dc.contributor.department | Chemistry | |
dc.date | 2018-02-17T07:57:03.000 | |
dc.date.accessioned | 2020-06-29T23:26:48Z | |
dc.date.available | 2020-06-29T23:26:48Z | |
dc.date.copyright | Fri Jan 01 00:00:00 UTC 1999 | |
dc.date.issued | 1999-10-01 | |
dc.description.abstract | <p>Among the reactions of hydrogen peroxide that are catalyzed by methyltrioxorhenium, the oxidation of alkylsilanes is unique. It is not a reaction in which an oxygen atom is added to a substrate, but one featuring a net insertion, R3Si−H + H2O2 → R3Si−OH + H2O. Kinetics studies were carried out on 10 compounds. Rate constant were determined for the bimolecular reaction of the silane with the peroxo compound CH3Re(O)(η2-O2)2(H2O). The variation of rate constant with the alkyl groups R follows two trends: the values of log(<em>k</em>) are linear functions of (a) the stretching frequency of the Si−H group and (b) the total Taft constant for these substituents. The reactions of (<em>n</em>-Bu)3Si−H and (<em>n</em>-Bu)3Si−D exhibit a kinetic isotope effect of 2.1 at 0 °C. From these data, a model for the transition state was formulated in which O−H and Si−O bond making accompany Si−H bond breaking. Quantum mechanical calculations have been carried out on the gas-phase reaction between Et3SiH and CH3Re(O)2(η2-O2). These results support this structure, calculating a structure and energy that are in agreement. The theoretical activation energy is 28.5 kcal mol-1, twice the experimental value in aqueous acetonitrile, 12.4 kcal mol-1. The difference can be attributed to the solvation of the polar transition state in this medium.</p> | |
dc.description.comments | <p>Reprinted (adapted) with permission from <em>Organometallics</em> 18 (1999): 4753, doi:<a href="http://dx.doi.org/10.1021/om990579d" target="_blank">10.1021/om990579d</a>. Copyright 1999 American Chemical Society.</p> | |
dc.format.mimetype | application/pdf | |
dc.identifier | archive/lib.dr.iastate.edu/ameslab_pubs/321/ | |
dc.identifier.articleid | 1323 | |
dc.identifier.contextkey | 7925366 | |
dc.identifier.s3bucket | isulib-bepress-aws-west | |
dc.identifier.submissionpath | ameslab_pubs/321 | |
dc.identifier.uri | https://dr.lib.iastate.edu/handle/20.500.12876/7881 | |
dc.language.iso | en | |
dc.source.bitstream | archive/lib.dr.iastate.edu/ameslab_pubs/321/0-L_1999_Gordon_ExperimentalTheoretical.pdf|||Fri Jan 14 23:35:05 UTC 2022 | |
dc.source.bitstream | archive/lib.dr.iastate.edu/ameslab_pubs/321/1999_Gordon_ExperimentalTheoretical.pdf|||Fri Jan 14 23:35:06 UTC 2022 | |
dc.source.uri | 10.1021/om990579d | |
dc.subject.disciplines | Chemistry | |
dc.title | Experimental and Theoretical Study of Oxygen Insertion into Trialkylsilanes by Methyltrioxorhenium Catalyst | |
dc.type | article | |
dc.type.genre | article | |
dspace.entity.type | Publication | |
relation.isAuthorOfPublication | 1a5927c0-5a5f-440e-86e0-9da8dc6afda0 | |
relation.isOrgUnitOfPublication | 25913818-6714-4be5-89a6-f70c8facdf7e | |
relation.isOrgUnitOfPublication | 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11 |
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