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Stereoselective "electrophilic" cyclometalation of planar-prochiral (eta(6)-arene)tricarbonylchromium complexes with asymmetric metal centers: pseudo-T-4 [Cp*RhCl2](2) and [Cp*IrCl2](2)
dc.creator | Scheeren, Carla | |
dc.creator | Maasarani, Fida | |
dc.creator | Hijazi, Akram | |
dc.creator | Đukić, Jean-Pierre | |
dc.creator | Pfeffer, Michel | |
dc.creator | Zarić, Snežana D. | |
dc.creator | Le Goff, Xavier-Frederic | |
dc.creator | Ricard, Louis | |
dc.date.accessioned | 2018-11-22T00:11:02Z | |
dc.date.available | 2018-11-22T00:11:02Z | |
dc.date.issued | 2007 | |
dc.identifier.issn | 0276-7333 | |
dc.identifier.uri | https://cherry.chem.bg.ac.rs/handle/123456789/843 | |
dc.description.abstract | The reactivity of a set of prototypical (eta(6)-arene)tricarbonylchromium complexes bearing amino, oxazolyl, and pyridyl ancillary ligands versus [Cp*RhCl2](2) and [Cp*IrCl2](2) has been investigated. Successful cyclometalation reactions were achieved essentially in the presence of hydrated sodium acetate with planar-prochiral 2-phenylpyridine and 3-methyl-2-phenylpyridine complexes with yields ranging from 60% to 92%. The most salient feature of the reported reactions is their stereoselectivity, as the only diastereomers to be produced are those with the Rh- and Ir-bound chloro ligand located trans with respect to the Cr(CO)(3). According to X-ray diffraction analyses, a relative rac-(pR,T-4-S) configuration may be assigned to the complexes: the Cp* ligand sits unexpectedly syn with respect to the tricarbonylmetal moiety. Introduction of the Cr(CO)(3) moiety by treatment of cycloiridated 2-phenylpyridine with tricarbonyl(eta(6)-naphthalene)chromium resulted in a unique diastereomer of the same relative configuration. Quantum calculations using the density functional theory were carried out on models of syn and trans-chloro isomers. Owing to strong electrostatic repulsion between the chloro ligand and the Cr(CO)(3) moiety, the syn-chloro isomers were found less stable by 7-8 kcal/mol than the trans counterparts, suggesting that cyclorhodation and cycloiridation reactions are thermodynamically controlled. | en |
dc.publisher | Amer Chemical Soc, Washington | |
dc.relation | info:eu-repo/grantAgreement/MESTD/MPN2006-2010/142037/RS// | |
dc.rights | restrictedAccess | |
dc.source | Organometallics | |
dc.title | Stereoselective "electrophilic" cyclometalation of planar-prochiral (eta(6)-arene)tricarbonylchromium complexes with asymmetric metal centers: pseudo-T-4 [Cp*RhCl2](2) and [Cp*IrCl2](2) | en |
dc.type | article | |
dc.rights.license | ARR | |
dcterms.abstract | Ле Гофф, Xавиер-Фредериц; Зарић, Снежана; Рицард, Лоуис; Пфеффер, Мицхел; Хијази, Aкрам; Дјукиц, Јеан-Пиерре; Маасарани, Фида; Сцхеерен, Царла; | |
dc.citation.volume | 26 | |
dc.citation.issue | 14 | |
dc.citation.spage | 3336 | |
dc.citation.epage | 3345 | |
dc.identifier.wos | 000247436400014 | |
dc.identifier.doi | 10.1021/om070170l | |
dc.citation.other | 26(14): 3336-3345 | |
dc.citation.rank | M21 | |
dc.type.version | publishedVersion | en |
dc.identifier.scopus | 2-s2.0-34547380846 |