Self-adaptable Catalysts: Substrate-Dependent Ligand Configuration

Self-adaptable Catalysts : Substrate-Dependent Ligand Configuration

QC20100524
Pd(II) allyl and Pd(0) olefin complexes containing the configurationally labile ligand 1,2-bis-[4,5dihydro-3H-dibenzo[c-e]azepino]ethane were studied as models for intermediates in Pd-catalyzed allylic alkylations. According to NMR and DFT studies, the ligand prefers C-s conformation in both eta(3)-1,3-diphenylpropenyl and eta(3)-cyclohexenyl Pd(II) complexes, whereas in Pd(0) olefin complexes it adopts different conformations in complexes derived from the two types of allyl systems in both solution and, as verified by X-ray crystallography, in the solid state. These results demonstrate that the Pd complex is capable of adapting its structure to the reacting substrate. The different structural preferences also provide an explanation for the behavior of 1,3-diphenyl-2-propenyl acetate and 2-cyclohexenyl acetate in Pd-catalyzed allylic alkylations using pseudo-C-2 and pseudo-C-s symmetric ligands.

Bouet, AlexisKTH,Organisk kemi,Christina Moberg(Swepub:kth)u18uqdec (författare)
Fjellander, Ester,1982-KTH,Organisk kemi,Christina Moberg(Swepub:kth)u114h0lr (författare)
Constant, SamuelUniversity of Geneva,Jérôme Lacour (författare)
Linder, DavidUniversity of Geneva,Jérôme Lacour (författare)
Andreas, FischerKTH,Oorganisk kemi,Andreas Fischer(Swepub:kth)u1mpcad5 (författare)
Lacour, JérômeUniversity of Geneva,Jérôme Lacour (författare)
Privalov, TimofeiKTH,Organisk kemi,Timofei Privalov(Swepub:kth)u1p555lx (författare)
Moberg, ChristinaKTH,Organisk kemi,Christina Moberg(Swepub:kth)u1dmzdbd (författare)
KTHOrganisk kemi (creator_code:org_t)

Ingår i:Journal of the American Chemical SocietyWashington DC : American Chemical Society130:6, s. 1845-18550002-78631520-5126

Av författaren/redakt...: Zalubovskis, Rai ...; Bouet, Alexis; Fjellander, Este ...; Constant, Samuel; Linder, David; Andreas, Fischer; visa fler...; Lacour, Jérôme; Privalov, Timofe ...; Moberg, Christin ...; visa färre...

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