A new method for modification of CN-palladacycles

Abstract

The reaction of benzylaminate CN palladacycle with chlorine dioxide was found to pro duce the 3 chlorine substituted analog through the formal insertion of chlorine into the Pd-C bond followed by repeated ortho palladation of the modified ligand. The structure of the resulting dimeric complex was confirmed by X ray diffraction study of its triphenylphosphine derivative. A comparison of the 1 H NMR spectra of the phosphine adducts of the starting and chlorinated complexes shows high conformational stability of the new palladacycle. Advan tages of the new route to conformational stabilization of labile palladacycles are discussed.

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.…”

Reactions of Cyclopalladated Complexes with Lithium Diphenylphosphide

“…The observed intramolecular trans-cyclopalladation is especially interesting considering that cyclopalladation of ( S C )-2,4-dibenzyl-2-oxazoline under different conditions results exclusively in the formation of CPC ( S C , S C )- 15 with the endo-palladacycle . However, this case of intramolecular trans-cyclopalladation is not unique; this type of transformation has been previously reported for other CPCs under different conditions. − …”

Reactions of m-chloroperoxybenzoic acid with dimeric cyclopalladated complexes derived from 2-phenyl-2-oxazolines

“…Reactions at the C-Pd bond of cyclopalladated complexes (CPCs) [1][2][3][4][5] (e.g., phosphination [6][7][8][9][10], chlorination [11][12][13][14], iodination [15][16][17][18][19], bromination [15,16], acetoxylation [20][21][22][23][24][25] and other transformations [15,[26][27][28][29][30][31]) represent an attractive method for highly regioselective functionalization of organic compounds. These Pd-mediated transformations are gaining importance as a synthetic method, providing access to new organic and organometallic compounds not readily available by other methods.…”