Coupling of the Triphenylphosphine Moiety to Water-Soluble Polymers: A New Method To Achieve Water-Soluble Metal Phosphine Complexes

Abstract

Coupling of methyl[4-(diphenylphosphino)benzyllamine to poly(acry1ic acid) and 4-(diphenylphos-phin0)benzaldehyde to polyethylenimine demonstrates a new method ofpreparing water-soluble phosphine ligands. The feasability of these polymeric ligands in complex formation is demonstrated by the preparation and characterization of water-soluble cobalt carbonyl complexes.Catalysis in biphasic media has emerged as an important method for achieving easier separation and reuse of homogeneous metal catalysts1 and its feasibility has been demonstrated by the Rhone-PoulendRuhrchemie hydroformylation process.2 The key prerequisite for carrying out homogeneous catalysis in aqueous solution is the use of a water-soluble ligand, a property usually achieved by functionalization of parent chiral or achiral, mono-or bidentate ligands with polar substituents, e.g.-OH , -COO-, -S03-, and -NRs+. While monosulfonated triphenylphosphine (TPPMS) marks a starting point in the development3 and application4 of watersoluble phosphine ligands, trisulfonated triphenylphosphine (TPPTS), with its extremely high water solubil-it^,^ can be regarded as the prototypical ligand in the field. Concomitant with improvements6 in the synthesis and purification of TPPTS, the coordination chemistry, as well as the catalytic chemistry, of TPPTS has pr~gressed.~ With respect to catalysis and coordination chemistry TPPTS complexes and their triphenylphos-

Nucleophilic Phosphanylation of Fluoroaromatic Compounds with Carboxyl, Carboxymethyl, and Aminomethyl Functionalities − an Efficient Synthetic Route to Amphiphilic Arylphosphanes

“…A new method for preparing water-soluble phosphanes by coupling of the phosphanylbenzylamine tionalized iodo-or bromo-aromatic compounds [1,12] . The electron impact mass spectra of the phosphane li-Ph 2 PϪC 6 H 4 ϪCH 2 Ϫ4-NH(Me) to polyacrylic acid has very recently been reported [18] . Attempts to prepare phosphanylgands with monocarboxylated phenyl groups (1Ϫ3, 5Ϫ7) all show the M ϩ peak.…”

Synthesis, characterisation and ligand properties of a new amphiphilic triphenylphosphine analogue †

“…The present work follows the second strategy and describes the synthesis and characterisation of the amphiphilic phosphine ligand {4-[bis(2-diethylaminoethyl)aminomethyl]-phenyl}diphenylphosphine (N3P) which can be regarded as a good model for the polyethyleneimine based ligand previously studied in our group. 18 It also describes new rhodium and platinum complexes employing N3P as a ligand, as well as an initial study of their properties in the homogeneous and biphasic hydroformylation of 1-hexene.…”

Phosphino-carboxamides: the inconspicuous gems

“…346 A similar ligand with a shorter linking group, PS-NHC(O)CH 2 CH 2 PPh 2 , was obtained from PS-NH 2 via acylation with acryloyl chloride and a subsequent addition of Ph 2 PH. 347 Andersson and co-workers reacted poly(acrylic acid) with an amine-substituted triphenylphosphine, 4-Ph 2 PC 6 H 4 CH 2 NH(Me), to obtain water-soluble macromolecular phosphines, 348 which were employed as ligands in Rh-catalysed hydrogenations 349 and hydroformylations. 350 The same method was used to immobilise chiral diphosphines through carbamate or urea units (see above).…”