Nucleophilicity of Neutral versus Cationic Magnesium Silyl Compounds

dc.contributor.author Yan, KaKing
dc.contributor.author Upton, Brianna
dc.contributor.author Sadow, Aaron
dc.contributor.author Zhu, Jing
dc.contributor.author Ellern, Arkady
dc.contributor.author Sadow, Aaron
dc.contributor.department Chemistry
dc.date 2018-02-17T07:01:00.000
dc.date.accessioned 2020-06-30T01:18:29Z
dc.date.available 2020-06-30T01:18:29Z
dc.date.copyright Tue Jan 01 00:00:00 UTC 2013
dc.date.embargo 2014-07-15
dc.date.issued 2013-07-15
dc.description.abstract <p>Charge and ancillary ligands affect the reactivity of monomeric tris(trimethylsilyl)silyl magnesium compounds. Diamine-coordinated (tmeda)Mg{Si(SiMe3)3}Me (tmeda = tetramethylethylenediamine; <strong>2-tmeda</strong>) and (dpe)Mg{Si(SiMe3)3}Me (dpe =1,2-<em>N</em>,<em>N</em>-dipyrrolidenylethane; <strong>2-dpe</strong>) are synthesized by salt elimination reactions of L2MgMeBr and KSi(SiMe3)3. Compounds <strong>2-tmeda</strong> or <strong>2-dpe</strong> react with MeI or MeOTf to give MeSi(SiMe3)3 as the product of Si–C bond formation. In contrast, <strong>2-tmeda</strong> and <strong>2-dpe</strong> undergo exclusively reaction at the magnesium methyl group with electrophiles such as Me3SiI, B(C6F5)3, HB(C6F5)2, and [Ph3C][B(C6F5)4]. These reactions provide a series of neutral, zwitterionic, and cationic magnesium silyl compounds, and from this series we have found that silyl group transfer is less effective with cationic magnesium compounds than neutral complexes.</p>
dc.description.comments <p>Reprinted (adapted) with permission from <em>Organometallics</em> 32 (2013): 6834, doi: <a href="http://dx.doi.org/10.1021/om400447q" target="_blank">10.1021/om400447q</a>. Copyright 2013 American Chemical Society.</p>
dc.format.mimetype application/pdf
dc.identifier archive/lib.dr.iastate.edu/chem_pubs/214/
dc.identifier.articleid 1221
dc.identifier.contextkey 7892547
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath chem_pubs/214
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/14656
dc.language.iso en
dc.source.bitstream archive/lib.dr.iastate.edu/chem_pubs/214/0-2013_SadowAD_NucleophilicityNeutralVersus.pdf|||Fri Jan 14 22:37:07 UTC 2022
dc.source.bitstream archive/lib.dr.iastate.edu/chem_pubs/214/2013_SadowAD_NucleophilicityNeutralVersus.pdf|||Fri Jan 14 22:37:08 UTC 2022
dc.source.uri 10.1021/om400447q
dc.subject.disciplines Chemistry
dc.subject.keywords Ancillary ligands
dc.subject.keywords Electrophiles
dc.subject.keywords elimination reaction
dc.subject.keywords neutral complexes
dc.subject.keywords nucleophilicities
dc.subject.keywords Si-C bond formation
dc.subject.keywords Tetramethylethylenediamine
dc.subject.keywords Trimethylsilyl
dc.subject.keywords magnesium
dc.title Nucleophilicity of Neutral versus Cationic Magnesium Silyl Compounds
dc.type article
dc.type.genre article
dspace.entity.type Publication
relation.isAuthorOfPublication a9d328ff-ec5e-4d1d-8c2f-aed9d5a290ed
relation.isOrgUnitOfPublication 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11
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