DC Field | Value | Language |
---|---|---|
dc.contributor.author | Oh, Seohee | ko |
dc.contributor.author | Kim, Seji | ko |
dc.contributor.author | Lee, Dayoung | ko |
dc.contributor.author | Gwak, Jinseong | ko |
dc.contributor.author | Lee, Yunho | ko |
dc.date.accessioned | 2017-01-13T05:02:39Z | - |
dc.date.available | 2017-01-13T05:02:39Z | - |
dc.date.created | 2016-12-19 | - |
dc.date.created | 2016-12-19 | - |
dc.date.created | 2016-12-19 | - |
dc.date.issued | 2016-12 | - |
dc.identifier.citation | INORGANIC CHEMISTRY, v.55, no.24, pp.12863 - 12871 | - |
dc.identifier.issn | 0020-1669 | - |
dc.identifier.uri | http://hdl.handle.net/10203/218744 | - |
dc.description.abstract | Two pathways of alkoxide migration occurring at a nickel(II) center supported by a PPP ligand (PPP- = P[2-(PPr2)-Pr-i-C6H4](2) ) are presented in this Article. In the first route, the addition of a pi-acidic ligand to a (PPP)Ni alkoxide species reveals the formation of a PO bond. This reaction occurs via metalligand cooperation (MLC) involving a 2-electron reduction at nickel. To demonstrate a PO bond formation, a nickel(II) isopropoxide species (PPP)Ni((OPr)-Pr-i) (4) was prepared. Upon addition of a pi-acidic isocyanide ligand (CNBu)-Bu-t, a nickel(0) isocyanide species ((PPP)-P-OiPr)Ni((CNBu)-Bu-t) (6b) was generated; PO bond formation occurred via reductive elimination (RE). When CO is present, migratory insertion (MI) occurs instead. The reaction of 4 with CO(g) results in the formation of (PPP)Ni((COOPr)-Pr-i) (5), representing an alternative pathway. The corresponding RE product ((PPP)-P-OiPr)Ni(CO) (6a) can be independently produced from the substitution reaction of {((PPP)-P-OiPr)Ni}(2)(mu-N-2) (3) with CO(g). While two different carbonylation pathways in 4 seem feasible, CO bond forming migratory insertion singly occurs. Regeneration of a (PPP)Ni moiety via a PO bond cleavage was demonstrated by treating 3 with CO2(g). The formation of (PPP)Ni((OCOOPr)-Pr-i) (7) clearly shows that an isopropoxide group migrates onto the bound CO2 ligand, and a PNi moiety is regenerated. | - |
dc.language | English | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.subject | N-HETEROCYCLIC PHOSPHENIUM | - |
dc.subject | REDOX-ACTIVE LIGANDS | - |
dc.subject | H OXIDATIVE ADDITION | - |
dc.subject | BOND ACTIVATION | - |
dc.subject | CATALYTIC-HYDROGENATION | - |
dc.subject | ISOCYANIDE INSERTION | - |
dc.subject | CARBENE COMPLEXES | - |
dc.subject | PINCER COMPLEXES | - |
dc.subject | TRIS-ISOCYANIDE | - |
dc.subject | CARBON BOND | - |
dc.title | Alkoxide Migration at a Nickel(II) Center Induced by a pi-Acidic Ligand: Migratory Insertion versus Metal-Ligand Cooperation | - |
dc.type | Article | - |
dc.identifier.wosid | 000390294600047 | - |
dc.identifier.scopusid | 2-s2.0-85006789515 | - |
dc.type.rims | ART | - |
dc.citation.volume | 55 | - |
dc.citation.issue | 24 | - |
dc.citation.beginningpage | 12863 | - |
dc.citation.endingpage | 12871 | - |
dc.citation.publicationname | INORGANIC CHEMISTRY | - |
dc.identifier.doi | 10.1021/acs.inorgchem.6b02226 | - |
dc.contributor.localauthor | Lee, Yunho | - |
dc.contributor.nonIdAuthor | Lee, Dayoung | - |
dc.description.isOpenAccess | N | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordPlus | N-HETEROCYCLIC PHOSPHENIUM | - |
dc.subject.keywordPlus | REDOX-ACTIVE LIGANDS | - |
dc.subject.keywordPlus | H OXIDATIVE ADDITION | - |
dc.subject.keywordPlus | BOND ACTIVATION | - |
dc.subject.keywordPlus | CATALYTIC-HYDROGENATION | - |
dc.subject.keywordPlus | ISOCYANIDE INSERTION | - |
dc.subject.keywordPlus | CARBENE COMPLEXES | - |
dc.subject.keywordPlus | PINCER COMPLEXES | - |
dc.subject.keywordPlus | TRIS-ISOCYANIDE | - |
dc.subject.keywordPlus | CARBON BOND | - |
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.