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Chemistry of palladium phosphinite (PPh2(OR)) and phosphonite (P(OPh)2(OH)) complexes: catalytic activity in methoxycarbonylation and Heck coupling reactions.

Autorzy

Iweta Pryjomska-Ray

Hubert Bartosz-Bechowski

Zbigniew Ciunik

Anna M. Trzeciak

Józef J. Ziółkowski

Rok wydania

2006

Czasopismo

Dalton Transactions

Strony

213-220

DOI

10.1039/B512835H

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

The new phosphinite and phosphonite complexes (1–8) are very efficient catalysts for the methoxycarbonylation of iodobenzene and Heck cross-coupling of bromobenzene with butyl acrylate. High catalytic activity of these complexes can be explained by their in situ transformations during the reaction, stimulated by the presence of water, acid (HCl) or base (NEt3). Hydrolysis of phosphinite palladium complexes of the form trans-PdCl2[PPh2(OR)]2 (R = C6F52, tBu 3, or O-menthyl 4) results in the formation of the dimeric complex [μ-ClPd(PPh2OH)(PPh2O)]25, which is deprotonated by NEt3, producing a polymeric complex of formula [Pd(P(O)PPh2)2]n8. The reverse reaction, protonolysis of 8 with HCl, leads back to 5 and the monomeric complex 5a. The phosphinite complex PdCl2[PPh2(OBu)]21 with a more lipophilic ligand, PPh2(OBu), does not undergo hydrolysis under the same conditions. In the reaction of PdCl2(cod) with P(OPh)2(OH), the new dimer [μ-ClPd(P(OPh)2OH)(P(OPh)2O)]26 was obtained, whereas reaction of Pd(OAc)2 with P(OPh)2(OH) leads to the polymeric complex [Pd[P(O)(OPh)2]2]n7. Protonolysis of 7 with HCl results in the formation of 6.

Adres publiczny

http://dx.doi.org/10.1039/B512835H

Strona internetowa wydawcy

https://www.rsc.org/

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