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Equilibrium Study of Pd(dba)(2) and P(OPh)(3) in the Pd-Catalyzed Allylation of Aniline by Allyl Alcohol
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för material- och miljökemi (MMK), Avdelningen för oorganisk kemi och strukturkemi.
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2014 (engelsk)Inngår i: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 33, nr 1, s. 249-253Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

Reaction of Pd(dba)(2) and P(OPh)(3) shows a unique equilibrium where the Pd[P(OPh)(3)](3) complex is favored over both Pd(dba)[P(OPh)(3)](2) and Pd[P(OPh)(3)](4) complexes at room temperature. At a lower temperature, Pd[P(OPh)(3)](4) becomes the most abundant complex in solution. X-ray studies of Pd[P(OPh)(3)](3) and Pd(dba)[P(OPh)(3)](2) complexes show that both complexes have a trigonal geometry with a Pd-P distance of 2.25 angstrom due to the pi-acidity of the phosphite ligand. In solution, pure Pd(dba)[P(OPh)(3)](2) complex equilibrates to the favored Pd[P(OPh)(3)](3) complex, which is the most stable complex of those studied, and also forms the most active catalytic species. This catalyst precursor dissociates one ligand to give the reactive Pd[P(OPh)(3)](2), which performs an oxidative addition of nonmanipulated allyl alcohol to generate the pi-allyl-Pd[P(OPh)(3)](2) intermediate according to ESI-MS

sted, utgiver, år, opplag, sider
2014. Vol. 33, nr 1, s. 249-253
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URN: urn:nbn:se:su:diva-100859DOI: 10.1021/om4009873ISI: 000329879900029OAI: oai:DiVA.org:su-100859DiVA, id: diva2:698223
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AuthorCount:5;

Tilgjengelig fra: 2014-02-20 Laget: 2014-02-17 Sist oppdatert: 2017-12-06bibliografisk kontrollert

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