Lewis Acid-Mediated β-Hydride Abstraction Reactions of Divalent M(C(SiHMe2)3)2THF2 (M = Ca, Yb)
| dc.contributor.author | Yan, KaKing | |
| dc.contributor.author | Upton, Brianna | |
| dc.contributor.author | Ellern, Arkady | |
| dc.contributor.author | Sadow, Aaron | |
| dc.contributor.author | Sadow, Aaron | |
| dc.contributor.department | Ames National Laboratory | |
| dc.contributor.department | Chemistry | |
| dc.date | 2018-02-17T07:02:52.000 | |
| dc.date.accessioned | 2020-06-30T01:18:35Z | |
| dc.date.available | 2020-06-30T01:18:35Z | |
| dc.date.copyright | Thu Jan 01 00:00:00 UTC 2009 | |
| dc.date.embargo | 2010-10-01 | |
| dc.date.issued | 2009-10-01 | |
| dc.description.abstract | <p>The divalent calcium and ytterbium compounds M(C(SiHMe2)3)2THF2 contain β-agostic SiH groups, as determined by spectroscopy and crystallography. Upon thermolysis, HC(SiHMe2)3is formed. However, the SiH groups are hydridic. The compounds M(C(SiHMe2)3)2THF2 react with 1 and 2 equiv of the Lewis acid B(C6F5)3 to form MC(SiHMe2)3HB(C6F5)3)THF2 and M(HB(C6F5)3)2THF2, respectively. These species contain the anion [HB(C6F5)3]− from hydride abstraction rather than [(Me2HSi)3CB(C6F5)3]− from alkyl abstraction. The 1,3-disilacyclobutane byproduct initially suggested β-elimination [as the dimer of the silene Me2Si═C(SiHMe2)2], but the other products and reaction stoichiometry rule out that pathway. Additionally, Yb(C(SiHMe2)3)2THF2 and the weak Lewis acid BPh3 react rapidly and also give the H-abstracted products. Despite the strong hydridic character of the SiH groups and the low-coordinate, Lewis acidic metal center in M(C(SiHMe2)3THF2 compounds, β-elimination is not an observed reaction pathway.</p> | |
| dc.description.comments | <p>Reprinted (adapted) with permission from <em>Journal of the American Chemical Society</em> 131 (2009): 15110, doi: <a href="http://dx.doi.org/10.1021/ja9070865" target="_blank">10.1021/ja9070865</a>. Copyright 2009 American Chemical Society.</p> | |
| dc.format.mimetype | application/pdf | |
| dc.identifier | archive/lib.dr.iastate.edu/chem_pubs/228/ | |
| dc.identifier.articleid | 1233 | |
| dc.identifier.contextkey | 7895777 | |
| dc.identifier.s3bucket | isulib-bepress-aws-west | |
| dc.identifier.submissionpath | chem_pubs/228 | |
| dc.identifier.uri | https://dr.lib.iastate.edu/handle/20.500.12876/14668 | |
| dc.language.iso | en | |
| dc.source.bitstream | archive/lib.dr.iastate.edu/chem_pubs/228/0-2009_SadowAD_LewisAcidMediated.pdf|||Fri Jan 14 22:44:35 UTC 2022 | |
| dc.source.bitstream | archive/lib.dr.iastate.edu/chem_pubs/228/2009_SadowAD_LewisAcidMediated.pdf|||Fri Jan 14 22:44:37 UTC 2022 | |
| dc.source.uri | 10.1021/ja9070865 | |
| dc.subject.disciplines | Chemistry | |
| dc.subject.keywords | chemical equations | |
| dc.subject.keywords | hydride abstraction | |
| dc.subject.keywords | Lewis Acid | |
| dc.subject.keywords | metal centers | |
| dc.subject.keywords | reaction pathways | |
| dc.subject.keywords | calcium | |
| dc.subject.keywords | chemical reactions | |
| dc.subject.keywords | crystallography | |
| dc.subject.keywords | hysteresis motors | |
| dc.subject.keywords | stoichiometry | |
| dc.subject.keywords | Ytterbium | |
| dc.subject.keywords | alkyl group | |
| dc.subject.keywords | cyclobutane derivative | |
| dc.subject.keywords | hydrogen | |
| dc.subject.keywords | infrared spectroscopy | |
| dc.subject.keywords | proton nuclear magnetic resonance | |
| dc.title | Lewis Acid-Mediated β-Hydride Abstraction Reactions of Divalent M(C(SiHMe2)3)2THF2 (M = Ca, Yb) | |
| dc.type | article | |
| dc.type.genre | article | |
| dspace.entity.type | Publication | |
| relation.isAuthorOfPublication | a9d328ff-ec5e-4d1d-8c2f-aed9d5a290ed | |
| relation.isOrgUnitOfPublication | 25913818-6714-4be5-89a6-f70c8facdf7e | |
| relation.isOrgUnitOfPublication | 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11 |