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Structural NMR Studies on Aryl‐Substituted π‐Allyl–Pd(II) Complexes by Concerted Use of Gradient‐Based Experiments
Author(s) -
Malet Ramón,
MorenoMañas Marcial,
Pajuelo Francesca,
Parella Teodor,
Pleixats Roser
Publication year - 1997
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/(sici)1097-458x(199704)35:4<227::aid-omr69>3.0.co;2-6
Subject(s) - chemistry , aryl , cationic polymerization , allylic rearrangement , substituent , regioselectivity , proton nmr , isomerization , carbon 13 nmr , denticity , ligand (biochemistry) , stereochemistry , nuclear magnetic resonance spectroscopy , fluorine 19 nmr , chemical shift , two dimensional nuclear magnetic resonance spectroscopy , proton , computational chemistry , medicinal chemistry , crystallography , organic chemistry , alkyl , catalysis , crystal structure , biochemistry , receptor , physics , quantum mechanics
Complete 1 H and 13 C NMR assignments of several aryl‐substituted π‐allyl–Pd(II) complexes were achieved using modern gradient‐based 1D and 2D experiments. In addition, unambiguous 31 P assignments were readily made using an improved gradient‐enhanced 1 H– 31 P HMBC experiment from which the regiochemistry of cationic complexes containing asymmetric bidentate ligands could also be elucidated. The effect of the nature of the substituent on allylic proton and carbon chemical shifts is briefly evaluated. Finally, a partial π–σ–π isomerization mechanism is proposed taking into account some observed dynamic NMR processes which are largely dependent on the ligand nature of these complexes. © 1997 by John Wiley & Sons, Ltd.