Untitled

Synthesis and coordination properties of palladium(II) and platinum(II) complexes with phosphonated triphenylphosphine derivatives

“…Ambitions to use various ''field-proven'' homogeneous catalysts under aqueous and biphasic conditions made for the synthesis of a vast amount of phosphines modified by hydrophilic groups such as ammonium and phosphonium (cationic), sulfonate, phosphonate and carboxylate (anionic) or alcohol and polyether chain (neutral) [1]. Phosphines modified by phosphonate moiety [2] have been attracting attention as alternatives to well-established sulfonates [1]; several examples of their use in biphasic catalysis have been mentioned in literature [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] (e.g., Pd-catalysed electrochemical reduction of CO 2 [3], Rh-catalysed carbon-carbon double bond hydrogenation or hydroformylation [4,5], Pd-catalysed benzyl halide carbonylation [6] and Suzuki coupling [7]). A great advantage (compared with other hydrophilic moieties) is the possibility to bind the phosphonated ligand to an inert oxide surface (e.g., Al 2 O 3 ) [8], onto activated carbon surface [9] or into a layered framework, e.g., zirconium phosphonate [10,12] or zirconium phosphite/phosphonate hybrid material [13].…”

“…A great advantage (compared with other hydrophilic moieties) is the possibility to bind the phosphonated ligand to an inert oxide surface (e.g., Al 2 O 3 ) [8], onto activated carbon surface [9] or into a layered framework, e.g., zirconium phosphonate [10,12] or zirconium phosphite/phosphonate hybrid material [13]. Such supported catalysts have been successfully tested in Rhcatalysed alkene hydroformylation [12,14], Rh-catalysed methanol carbonylation [9,15], Ru-catalysed asymmetric b-keto ester hydrogenation [4,11] or Heck reaction [13]. Several tests were also performed in organic solvents under homogeneous conditions (e.g., Pt/Sn-catalysed alkene hydroformylation [11], Rh-catalysed methanol carbonylation [16] and Rh-catalysed styrene hydroformylation [17]).…”

“…The ortho and meta isomers of 3a and 4a (and their disodium salts) were already reported by Liek et al [7] having been used as catalysts in Pd-catalysed Suzuki coupling under biphasic conditions with satisfactory results. Later, also the para isomer has been mentioned [14] in a set of phosphanyl-phosphonates (including 4a and its disodium salt) and experiments on Rh-catalyzed hydroformylation were performed, but no details on characterization of the complexes were mentioned and no attention to Pd(II) and Pt(II) chemistry was paid. To our knowledge, ligands 3b and 4b have not been reported yet.…”

ChemInform Abstract: Synthesis and Characterization of 4‐ and 4,4′‐Phosphorylated 2,2′‐Bis(diphenylphosphanyl)‐1,1′‐binaphthyls.

“…[14Ϫ16] Phosphorylated alkyldiarylphosphanes showed an outstanding performance in the hydroformylation of higher terminal olefins [14] in aqueous biphasic systems, which offer several technological advantages, [2,3] especially simplified catalyst recycling. [14Ϫ16] Phosphorylated alkyldiarylphosphanes showed an outstanding performance in the hydroformylation of higher terminal olefins [14] in aqueous biphasic systems, which offer several technological advantages, [2,3] especially simplified catalyst recycling.…”

Synthesis and Characterization of 4- and 4,4′-Phosphorylated2,2′-Bis(diphenylphosphanyl)-1,1′-binaphthyls

“…During our investigations on hydroformylation in aqueous biphasic systems and over heterogenized complexes we succeeded in the functionalization of a series of tertiary aryl‐ and arylalkylphosphanes with phosphonate groups 14−16. Phosphorylated alkyldiarylphosphanes showed an outstanding performance in the hydroformylation of higher terminal olefins14 in aqueous biphasic systems, which offer several technological advantages,2,3 especially simplified catalyst recycling. To expand the application field of phosphorylated ligands to asymmetric hydroformylation in biphasic systems, we developed new methods to introduce phosphonate groups to a well‐known atropisomeric ligand — BINAP [2,2′‐bis(diphenylphosphanyl)‐1,1′‐binaphthyl] — as described below.…”