Chemoselective methoxycarbonylation of terminal alkynes catalyzed by Pd(II)-TROPP complexes (Articolo in rivista)

Type

• Articolo in rivista (Classe)
• Prodotto della ricerca (Classe)

Label

• Chemoselective methoxycarbonylation of terminal alkynes catalyzed by Pd(II)-TROPP complexes (Articolo in rivista) (literal)

Anno

• 2010-01-01T00:00:00+01:00 (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi

• 10.1039/c002976a (literal)

Alternative label

• Bettucc,i Lorenzo; Bianchini, Claudio; Oberhauser, Werner; Vogt, Matthias; Grützmacher, Hansjoerg (2010)
  Chemoselective methoxycarbonylation of terminal alkynes catalyzed by Pd(II)-TROPP complexes
  in Dalton transactions (2003. Print)
  (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori

• Bettucc,i Lorenzo; Bianchini, Claudio; Oberhauser, Werner; Vogt, Matthias; Grützmacher, Hansjoerg (literal)

Pagina inizio

• 6509 (literal)

Pagina fine

• 6417 (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume

• 39 (literal)

Rivista

• Dalton transactions (Rivista)

Note

• ISI Web of Science (WOS) (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni

• ICCOM-CNR ETH Zuerich (literal)

Titolo

• Chemoselective methoxycarbonylation of terminal alkynes catalyzed by Pd(II)-TROPP complexes (literal)

Abstract

• The mono-phosphanes 5-(diphenyl)-phosphanyl-5H-dibenzo[a,d]cycloheptene (TROPPPh) and 5-((2-methoxy)phenyl)-phosphanyl-5H-dibenzo[a,d]cycloheptene (TROPP(2-MeOPh)) have been employed to coordinate PdCl2, yielding [PdCl2(TROPPPh)] (1a) and [PdCl2(TROPP(2-MeOPh))] (1b), respectively. The corresponding tosylate (OTs) complexes [Pd(OTs)2(TROPPPh)] (2a) and [Pd(OTs)2(TROPP(2-MeOPh))] (2b) have been successfully applied in the p-benzoquinone (BQ)-assisted methoxycarbonylation of terminal alkynes to give chemoselectively the corresponding alkynylcarboxylic acid methyl ester with high TOF (up to 980 h-1). Unlike 2a/b, the PdII-(tosylate)-diphosphane complexes [Pd(OTs)(H2O)(dppp)](OTs) 2c (dppp = 1,3-bis-di(phenylphosphanyl)propane and [Pd(H2O)2(MeO-dppp)](OTs)2 2d (MeO-dppp = 1,3-bis(di(2-methoxyphenyl)phosphanyl)propane) preferentially catalyzed a double alkyne insertion. The \"in situ\" spectroscopic observation of the Pd-methoxycarbonyl compound [Pd(COOMe)(TROPPPh)](OTs) (3a) in conjunction with the evidence of the fast b-hydride elimination reaction of TROPP-based Pd-catalysts in the dimerization reaction of ethene are indicative for a strongly electrophilic metal centre. The X-ray crystal structures of 1a·0.5C2H4Cl2 and of the neutral and cationic Pd-alkyl complexes [Pd(Me)(Cl)(TROPPPh) (7a·0.5CH2Cl2) and [Pd(CH2CH2COMe)- (TROPPPh)](PF6) (10a·0.5C6H6), respectively, confirm unambiguously the bidentate coordination mode of TROPP-ligands to PdII, that persists even in the presence of CO pressure. (literal)

Prodotto di

• Istituto di chimica dei composti organo metallici (ICCOM) (Istituto)
• Catalisi ed elettrocatalisi per la produzione sostenibile di energia e la trasformazione di risorse rinnovabili (PM.P03.001.001) (Modulo)

Autore CNR

• Lorenzo Bettucci (Persona)
• CLAUDIO BIANCHINI (Persona)
• WERNER OBERHAUSER (Unità di personale interno)

Incoming links:

Prodotto

• Istituto di chimica dei composti organo metallici (ICCOM) (Istituto)
• Catalisi ed elettrocatalisi per la produzione sostenibile di energia e la trasformazione di risorse rinnovabili (PM.P03.001.001) (Modulo)

Autore CNR di

• CLAUDIO BIANCHINI (Persona)
• WERNER OBERHAUSER (Unità di personale interno)
• Lorenzo Bettucci (Persona)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#rivistaDi

• Dalton transactions (Rivista)