Exploiting the π-Acceptor Properties of Carbene-Stabilized Phosphorus Centered Trications [LP] : Applications in Pt(II) Catalysis.
Reaction of tris(dimethylaminocyclopropenium) substituted phosphine 1 with KPtCl afforded the bench stable complex 3 which upon treatment with Ag[CBHCl] turned out to be an excellent catalyst for the transformation of a variety of ortho-biaryl substituted alkynes into polycyclic homo- and heteroaren...
| Publicado en: | Journal of the American Chemical Society Vol. 134; no. 40; pp. 16753 - 16759 |
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| Autores principales: | , , , |
| Formato: | Artículo |
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American Chemical Society
10/10/2012
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| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=82677134&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 82677134 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 10/10/2012 vid: 134 iid: 40 pid: 997 pub: American Chemical Society artinfo: ui: 82677134 10.1021/ja306947m ppf: 16753 ppct: 6 formats: tig: atl: Exploiting the π-Acceptor Properties of Carbene-Stabilized Phosphorus Centered Trications [LP] : Applications in Pt(II) Catalysis. aug: au: Carreras, Javier Patil, Mahendra Thiel, Walter Alcarazo, Manuel affil: Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-45470 Mülheim an der Ruhr, Germany su: Carbenes Cations Phosphorus Density functionals Phosphorus compounds Surface chemistry sug: subj: Carbenes Cations Phosphorus Density functionals Phosphorus compounds Surface chemistry ab: Reaction of tris(dimethylaminocyclopropenium) substituted phosphine 1 with KPtCl afforded the bench stable complex 3 which upon treatment with Ag[CBHCl] turned out to be an excellent catalyst for the transformation of a variety of ortho-biaryl substituted alkynes into polycyclic homo- and heteroarenes of different size, shape, and curvature through a 6-endo-dig cyclization. This constitutes the first example ever reported of using a P-centered trication as ligand in catalysis. The strong π-acceptor character of 1 that derives from its three positive charges substantially increases the intrinsic π-acidity of Pt in complex 1·PtCl and dramatically enhances its ability to activate π-systems toward nucleophilic attack. As a consequence, a remarkable acceleration of the model transformation is observed when compared with other classical π-acceptor ligands such as P(OPh) or P(CF). Moreover, the employment of 1 as ligand also expands the scope of this reaction to previously inaccessible substitution patterns. Kinetic studies and deuterium labeling experiments as well as density functional theory (DFT) calculations were performed in order to explain these findings. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2012 holdings: @attributes: islocal: N |
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