DC Field | Value | Language |
---|---|---|
dc.contributor.author | Jafari, Mehrafshan G. | ko |
dc.contributor.author | Park, Yerin | ko |
dc.contributor.author | Pudasaini, Bimal | ko |
dc.contributor.author | Kurogi, Takashi | ko |
dc.contributor.author | Carroll, Patrick J. | ko |
dc.contributor.author | Kaphan, David M. | ko |
dc.contributor.author | Kropf, Jeremy | ko |
dc.contributor.author | Delferro, Massimiliano | ko |
dc.contributor.author | Baik, Mu-Hyun | ko |
dc.contributor.author | Mindiola, Daniel J. | ko |
dc.date.accessioned | 2021-11-19T06:40:29Z | - |
dc.date.available | 2021-11-19T06:40:29Z | - |
dc.date.created | 2021-10-18 | - |
dc.date.created | 2021-10-18 | - |
dc.date.created | 2021-10-18 | - |
dc.date.issued | 2021-11 | - |
dc.identifier.citation | ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, v.60, no.46, pp.24411 - 24417 | - |
dc.identifier.issn | 1433-7851 | - |
dc.identifier.uri | http://hdl.handle.net/10203/289275 | - |
dc.description.abstract | A low-spin and mononuclear vanadium complex, ((Me)nacnac)V(CO)(eta(2)-P equivalent to(CBu)-Bu-t) (2) ((Me)nacnac(-)=[ArNC(CH3)](2)CH, Ar=2,6-(Pr2C6H3)-Pr-i), was prepared upon treatment of the vanadium neopentylidyne complex ((Me)nacnac)V equivalent to(CBu)-Bu-t(OTf) (1) with Na(OCP)(diox)(2.5) (diox=1,4-dioxane), while the isoelectronic ate-complex [Na(15-crown-5)]{([ArNC(CH2)]CH[C(CH3)NAr])V(CO)(eta(2)-P equivalent to(CBu)-Bu-t)} (4), was obtained via the reaction of Na(OCP)(diox)(2.5) and ([ArNC(CH2)]CH[C(CH3)NAr])V equivalent to(CBu)-Bu-t(OEt2) (3) in the presence of crown-ether. Computational studies suggest that the P-atom transfer proceeds by [2+2]-cycloaddition of the P equivalent to C bond across the V equivalent to(CBu)-Bu-t moiety, followed by a reductive decarbonylation to form the V-C equivalent to O linkage. The nature of the electronic ground state in diamagnetic complexes, 2 and 4, was further investigated both theoretically and experimentally, using a combination of density functional theory (DFT) calculations, UV/Vis and NMR spectroscopies, cyclic voltammetry, X-ray absorption spectroscopy (XAS) measurements, and comparison of salient bond metrics derived from X-ray single-crystal structural characterization. In combination, these data are consistent with a low-valent vanadium ion in complexes 2 and 4. This study represents the first example of a metathesis reaction between the P-atom of [PCO](-) and an alkylidyne ligand. | - |
dc.language | English | - |
dc.publisher | WILEY-V C H VERLAG GMBH | - |
dc.title | Phosphorus-Atom Transfer from Phosphaethynolate to an Alkylidyne | - |
dc.type | Article | - |
dc.identifier.wosid | 000704324900001 | - |
dc.identifier.scopusid | 2-s2.0-85116424550 | - |
dc.type.rims | ART | - |
dc.citation.volume | 60 | - |
dc.citation.issue | 46 | - |
dc.citation.beginningpage | 24411 | - |
dc.citation.endingpage | 24417 | - |
dc.citation.publicationname | ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | - |
dc.identifier.doi | 10.1002/anie.202107475 | - |
dc.embargo.liftdate | 9999-12-31 | - |
dc.embargo.terms | 9999-12-31 | - |
dc.contributor.localauthor | Baik, Mu-Hyun | - |
dc.contributor.nonIdAuthor | Jafari, Mehrafshan G. | - |
dc.contributor.nonIdAuthor | Pudasaini, Bimal | - |
dc.contributor.nonIdAuthor | Kurogi, Takashi | - |
dc.contributor.nonIdAuthor | Carroll, Patrick J. | - |
dc.contributor.nonIdAuthor | Kaphan, David M. | - |
dc.contributor.nonIdAuthor | Kropf, Jeremy | - |
dc.contributor.nonIdAuthor | Delferro, Massimiliano | - |
dc.contributor.nonIdAuthor | Mindiola, Daniel J. | - |
dc.description.isOpenAccess | N | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordAuthor | alkylidyne | - |
dc.subject.keywordAuthor | diketiminate | - |
dc.subject.keywordAuthor | phosphaalkyne | - |
dc.subject.keywordAuthor | phosphorus | - |
dc.subject.keywordAuthor | vanadium | - |
dc.subject.keywordPlus | SODIUM PHOSPHAETHYNOLATE | - |
dc.subject.keywordPlus | CONVENIENT SYNTHESIS | - |
dc.subject.keywordPlus | BUILDING-BLOCKS | - |
dc.subject.keywordPlus | COMPLEXES | - |
dc.subject.keywordPlus | VANADIUM | - |
dc.subject.keywordPlus | ANION | - |
dc.subject.keywordPlus | REACTIVITY | - |
dc.subject.keywordPlus | NA(OCP) | - |
dc.subject.keywordPlus | CP | - |
dc.subject.keywordPlus | PHOSPHAKETENES | - |
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