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Nachweis von π → σ‐Umlagerungen bei Ligandenverdrängungsreaktionen von π‐Allyl‐π‐cyclopentadienyl‐Palladiumkomplexen
Author(s) -
Parker Graham,
Werner Helmut
Publication year - 1973
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19730560816
Subject(s) - chemistry , cyclopentadiene , allylic rearrangement , cyclopentadienyl complex , ligand (biochemistry) , medicinal chemistry , lewis acids and bases , stereochemistry , catalysis , organic chemistry , receptor , biochemistry
It has been proved by NMR. measurements at low temperatures that the ligand displacement reactions of (π‐all)Pd(π‐C 5 H 5 ) and Lewis bases L yielding PdL 4 proceed by a π → σ rearrangement of the allylic group as the primary step. The organic reaction product is the 1‐isomer of the corresponding allylcyclopentadiene but in the reactions of (π‐1,1,2‐Me 3 C 3 H 2 )Pd(π‐C 5 H 5 ) with L besides the isomeric allylcyclopentadienes also 2,3‐dimethylbutadiene and cyclopentadiene are formed. The reaction mechanism will be discussed.

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