Self-Organized Nanosalts of Pd(II)-Ammonium-Tethered Carboxylic Acid for the Synthesis of Antifouling Polyketones

Abstract

Pd­(II) nanosalts formed from [LnPd­(OAc)2] (Ln = 1,3-bis­(di-o-methoxyphenylphosphino)­propane) and ammonium tethered carboxylic acids in MeOH were utilized for the synthesis of antifouling polyketones from CO and olefin; this is the first instance of the synthesis of antifouling polyketones in the absence of additional heterogeneous seeds. The polymerization of CO and olefin achieved with the in situ-generated Pd­(II) nanosalts was studied, and the nanosalts were analyzed by dynamic light scattering (DLS) experiments.

Tandem Pauson‐Khand Reaction Using Carbon Dioxide as the C1‐Source

“…Carbon monoxide is an important substrate widely applied by the chemical industry in the synthesis of both bulk and fine chemicals. [1][2][3][4][5][6][7] However, CO is highly toxic and demands special handling, and consequently alternative ways of introducing the CO synthon in organic molecules are under investigation. [8] One method consists of the in situ generation of CO from other species followed by its subsequent reaction.…”

(Iminopyridine)Pd (II) complexes as versatile catalysts for copolymerization and terpolymerization of vinyl arene, ethylene, and carbon monoxide

“…Our research group previously developed highly efficient palladium catalysts for the synthesis of polyketone from ethylene and CO. [ 21–24 ] Yet the diphosphine ligands used in our previous work do not efficiently introduce aromatic alkenes into polyketone chains that comprise ethylene and CO. Thus, we explored the utility of amine ligand‐modified palladium catalysts for this purpose.…”

Template‐free anion‐controlled synthesis of Pd (II) nano‐aggregates for the antifouling polymerization of CO and ethylene

“…Subsequent reduction of the palladium ions to palladium metal inside the template affords palladium metal nanocatalysts. In contrast to studies on nano‐sized palladium (0) metal catalysts, the synthesis and catalytic application of nano‐sized palladium (II) catalysts have been rarely investigated . Considering the interesting effects of Pd (II) catalysts, the use of Pd (II) nanocatalysts in a range of organic reactions would represent a novel strategy for Pd (II)‐catalyzed reactions …”

“…To resolve the reactor fouling issue, heterogeneous seeds or heterogeneous catalysts have been adopted . Recently, our research group developed an innovative approach to prevent polymer agglomeration without using exogenous heterogeneous materials . The reaction of carboxylic acid‐functionalized imidazolium salts with Pd (II) complexes afforded highly dispersed Pd (II) aggregates in the absence of a template, where polymer growth was controlled by nano‐sized Pd (II) aggregates, resulting in the successful inhibition of reactor fouling (Scheme ).…”

“…The reaction of carboxylic acid‐functionalized imidazolium salts with Pd (II) complexes afforded highly dispersed Pd (II) aggregates in the absence of a template, where polymer growth was controlled by nano‐sized Pd (II) aggregates, resulting in the successful inhibition of reactor fouling (Scheme ). Presumably, the reaction of carboxylic acid‐functionalized imidazolium bromides (pKa = 2.32) and [(domppp) Pd (OAc) 2 ] [domppp = 1,3‐bis (di‐ o ‐methoxyphenylphosphino)propane] induced substitution of acetate from [(domppp) Pd (OAc) 2 ] with less coordinating carboxylate‐functionalized imidazolium bromides. After substitution, catalytically active Pd (II) aggregates are suspended in the solution.…”