A resolution of the monodentate P*-chiral phosphine PButC6H4Br-4 and its NMR-deduced absolute configuration

Amidophosphine‐stabilized palladium complexes catalyse Suzuki–Miyaura cross‐couplings in aqueous media

“…The Pd1‐P1 bond distance in 7 of 2.2522(10) Å is similar to those observed in phosphine and phosphite complexes of Pd(II) (2.2–2.4 Å) and in neutral complex 1 (2.2543(9) Å) . The value of Pd1‐N1 bond length being 2.097(3) Å defines a strong coordination of N to Pd atom and is comparable to those found in similar monomeric N‐coordinated Pd complexes (2.073–2.155 Å) . The second nitrogen atom N2 of L 1 PPh 2 is protonated providing palladium cation cis ‐{[2‐(Me 2 NHCH 2 )‐6‐(Me 2 NCH 2 )C 6 H 3 ]Ph 2 P}PdCl 2 , that is compensated by Cl − anion.…”

Assignment of absolute configuration using chiral reagents and NMR spectroscopy

“…Similarly, an analogous palladium dimer with a bulky tert-butyl group on the alkyl portion of the palladacycle (123) has been used to assign absolute configuration of tert-butylphenyl(4-bromophenyl)phosphine through NOE connectivity data. 234 If the phosphine has a second binding site, such as the nitrogen atom in methylphenyl(8-quinolyl)phosphine (124) 235 or amine group of 125, 236 complexation to palladium involves chelate bonding. Differential shielding occurs in a manner consistent with the absolute configuration of the substrate.…”

P‐Chirogenic Benzo‐Fused Phenoxaphosphane: Synthesis, Resolution and Study of the Stereochemical Properties of the Corresponding Palladium Complexes

“…[23] The absolute configuration of the phosphorus atom, in compounds 7a,b, has been unambiguously assigned by complementing the study of the NOE( 1 H-1 H) contacts and the NMR chemical shift regularities with DFT calculations performed using SPARTAN. [23,24] scale, pointing out a totally different magnetic field experienced by this proton in the δ-λ conformations of the Pd-C-N ring. [17] Calculations at the HF-DFT SDF level of theory, using RB3LYP as method and LACVP* as basis set, have been carried out for the four most stable conformers 7, namely the structures containing the combination of the two different absolute configurations at the phosphorus atom R/S with the two possible conformations δ-λ of the palladacycles, (Figure 6).…”