TY - JOUR
T1 - (η3-phenylallyl)(phosphanyloxazoline)palladium complexes
T2 - X-ray crystallographic studies, NMR investigations, and Ab initio/DFT calculations
AU - Kollmar, Martin
AU - Steinhagen, Henning
AU - Janssen, Jörg P.
AU - Goldfuss, Bernd
AU - Malinovskaya, Svetlana A.
AU - Vázquez, Jordi
AU - Rominger, Frank
AU - Helmchen, Günter
PY - 2002/7/15
Y1 - 2002/7/15
N2 - All possible (η3-allyl)palladium complexes (1-4) of the ligand (4S)-[2-(2′-diphenylphosphanyl)phenyl]-4,5-dihydro-4-(2-propyl)-oxazole (L1) and η3-allyl ligands with one to three phenyl substituents at the terminal allylic centers were synthesized and characterized by x-ray crystal structure analysis and, with respect to allylic isomers, by NMR investigations. Equilibrium geometries, electronic structures, and relative energies of isomeric complexes were computed by restricted Hartree-Fock (RHF) and density functional theory (DFT) calculations; experimentally determined isomer ratios could be reproduced. The results allowed important conclusions to be drawn regarding the mechanism of Pd-catalyzed asymmetric allylic substitutions.
AB - All possible (η3-allyl)palladium complexes (1-4) of the ligand (4S)-[2-(2′-diphenylphosphanyl)phenyl]-4,5-dihydro-4-(2-propyl)-oxazole (L1) and η3-allyl ligands with one to three phenyl substituents at the terminal allylic centers were synthesized and characterized by x-ray crystal structure analysis and, with respect to allylic isomers, by NMR investigations. Equilibrium geometries, electronic structures, and relative energies of isomeric complexes were computed by restricted Hartree-Fock (RHF) and density functional theory (DFT) calculations; experimentally determined isomer ratios could be reproduced. The results allowed important conclusions to be drawn regarding the mechanism of Pd-catalyzed asymmetric allylic substitutions.
KW - Ab initio calculations
KW - Allyl ligands
KW - NMR spectroscopy
KW - Palladium
KW - Structure elucidation
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U2 - 10.1002/1521-3765(20020715)8:14<3103::AID-CHEM3103>3.0.CO;2-C
DO - 10.1002/1521-3765(20020715)8:14<3103::AID-CHEM3103>3.0.CO;2-C
M3 - Article
AN - SCOPUS:0037101666
SN - 0947-6539
VL - 8
SP - 3103
EP - 3114
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 14
ER -