223264-58-2Relevant academic research and scientific papers
Solution behavior and X-ray structure of cationic allylpalladium(II) complexes with iminophosphine ligands. Kinetics and mechanism of allyl amination by secondary amines
Crociani, Bruno
, p. 1137 - 1147 (2008/10/08)
The solution behavior of the cationic complexes [Pd(η3-allyl)(P-N)]+ (P-N = o-(PPh2)C6H4-CH=NR (R = C6H4OMe-4, Me, CMe3, (R)-bornyl); allyl = propenyl (1a-4a) and 3-methyl-2-butenyl (1b-4b)) consists essentially of three dynamic processes: (i) a very fast conformational change of the P-N chelate ring, which moves above and below the P-Pd-N coordination plane, (ii) a relatively fast η3-η1-η3 interconversion which brings about a syn-anti exchange only for the allylic protons cis to phosphorus; (iii) a slower apparent rotation of the η3-allyl ligand around its bond axis. For 1b-3b, two geometrical isomers are observed, the predominant one having the allyl CMe2 group trans to phosphorus. The complexes 4a and 4b, containing the chiral (R)-bornyl group, are present in solution with two and four diastereomeric species, respectively.
