DC Field | Value | Language |
---|---|---|
dc.contributor.author | Kurogi, Takashi | ko |
dc.contributor.author | Won, Joonghee | ko |
dc.contributor.author | Park, Bohyun | ko |
dc.contributor.author | Trofymchuk, Oleksandra S. | ko |
dc.contributor.author | Carroll, Patrick J. | ko |
dc.contributor.author | Baik, Mu-Hyun | ko |
dc.contributor.author | Mindiola, Daniel J. | ko |
dc.date.accessioned | 2018-05-24T02:44:01Z | - |
dc.date.available | 2018-05-24T02:44:01Z | - |
dc.date.created | 2018-05-14 | - |
dc.date.created | 2018-05-14 | - |
dc.date.created | 2018-05-14 | - |
dc.date.created | 2018-05-14 | - |
dc.date.created | 2018-05-14 | - |
dc.date.issued | 2018-04 | - |
dc.identifier.citation | CHEMICAL SCIENCE, v.9, no.13, pp.3376 - 3385 | - |
dc.identifier.issn | 2041-6520 | - |
dc.identifier.uri | http://hdl.handle.net/10203/242359 | - |
dc.description.abstract | C-H activation of methane followed by dehydrocoupling at room temperature led ultimately to the formation of the olefin H2C=(CHBu)-Bu-t via the addition of redox-active ligands (L) such as thioxanthone or 2,2'-bipyridine (bipy) to (PNP)Ti=(CHBu)-Bu-t(CH3) (1). Using both of these exogenous ligand systems, we could trap the titanium fragment via an insertion reaction with these two substrates to afford species of the type (PNP)Ti(L)(LH). A combination of computational and isotopic labeling studies reveals that the L ligand promotes the C-C bond forming step by migration of the methyl moiety in 1 to the alpha-alkylidene carbon by producing a Ti(III) species (PNP)Ti{CH(CH3)Bu-t}(L). In the case of L = thioxanthone, beta-hydrogen abstraction gives an olefin, whereas with 2,2'-bipyridine beta-hydride elimination and migratory insertion lead to (PNP)Ti(L)(LH). These redox-active ligands play two important roles: (i) they accept an electron from the Ti-alkylidene fragment to allow the methyl to approach the alkylidene and (ii) they serve as traps of a hydrogen atom resulting from olefin elimination. These systems represent the first homogeneous models that can activate methane and selectively dehydrocouple it with a carbene to produce an olefin at room temperature. | - |
dc.language | English | - |
dc.publisher | ROYAL SOC CHEMISTRY | - |
dc.title | Room temperature olefination of methane with titanium-carbon multiple bonds | - |
dc.type | Article | - |
dc.identifier.wosid | 000431113300015 | - |
dc.identifier.scopusid | 2-s2.0-85044717044 | - |
dc.type.rims | ART | - |
dc.citation.volume | 9 | - |
dc.citation.issue | 13 | - |
dc.citation.beginningpage | 3376 | - |
dc.citation.endingpage | 3385 | - |
dc.citation.publicationname | CHEMICAL SCIENCE | - |
dc.identifier.doi | 10.1039/c7sc05238c | - |
dc.contributor.localauthor | Baik, Mu-Hyun | - |
dc.contributor.nonIdAuthor | Kurogi, Takashi | - |
dc.contributor.nonIdAuthor | Trofymchuk, Oleksandra S. | - |
dc.contributor.nonIdAuthor | Carroll, Patrick J. | - |
dc.contributor.nonIdAuthor | Mindiola, Daniel J. | - |
dc.description.isOpenAccess | Y | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordPlus | FISCHER-TROPSCH SYNTHESIS | - |
dc.subject.keywordPlus | ORGANOMETALLIC CHEMISTRY | - |
dc.subject.keywordPlus | HYDRIDE COMPLEXES | - |
dc.subject.keywordPlus | CYCLIC ALKANES | - |
dc.subject.keywordPlus | METAL | - |
dc.subject.keywordPlus | DEHYDROGENATION | - |
dc.subject.keywordPlus | ACTIVATION | - |
dc.subject.keywordPlus | LIGAND | - |
dc.subject.keywordPlus | 2,2&apos | - |
dc.subject.keywordPlus | -BIPYRIDINE | - |
dc.subject.keywordPlus | METATHESIS | - |
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