Phosphines multidentate

Indeed, these reactions proceed at 25 °C in ethanol-aqueous media in the absence of transition metal catalysts. The ease with which P-H bonds in primary phosphines can be converted to P-C bonds, as shown in Schemes 9 and 10, demonstrates the importance of primary phosphines in the design and development of novel organophosphorus compounds. In particular, functionalized hydroxymethyl phosphines have become ubiquitous in the development of water-soluble transition metal/organometallic compounds for potential applications in biphasic aqueous-organic catalysis and also in transition metal based pharmaceutical development [53-62]. Extensive investigations on the coordination chemistry of hydroxymethyl phosphines have demonstrated unique stereospe-cific and kinetic propensity of this class of water-soluble phosphines [53-62]. Representative examples outlined in Fig. 4, depict bidentate and multidentate coordination modes and the unique kinetic propensity to stabilize various oxidation states of metal centers, such as Re( V), Rh(III), Pt(II) and Au(I), in aqueous media [53 - 62]. Therefore, the importance of functionalized primary phosphines in the development of multidentate water-soluble phosphines cannot be overemphasized. 

Pt(en)(N03)2] and [Pt(OTf)2L2] (L = mono- or 1/2 bidentate tertiary phosphine) or dinuclear complexes of the type [Pt2(OTf)2(/i-monodentate tertiary phosphine cr-aryl = 4, -biphenyl, / -terphenyL 4,4 -benzophenone, etc.) other structural motifs employing platinum(II) have also been reported.2 0 The addition of bridging, multidentate N-donor ligands of various shapes and sizes to the labile complexes in a suitable solvent system has afforded several classes of discrete, plat-inum(II)-containing polygons, polyhedra, and catenanes. 

Alternatively, bi- or multidentate ligands can also be used for support. As an additional benefit, the latter offer greater stability for the coordinatively bound metal center against leaching through ligand dissociation and substitution reactions. The first, somewhat remarkable, approach to this is shown in Figure 42.11, based on numerous examples of the support of bidentate phosphines on polymers [1-5]. 

Phosphines and arsines containing more than one olefinic group were neglected as possible multidentate ligands until Hall prepared the tris (orfAo-vinylphenyl) derivatives of phosphorus, arsenic and antimony (tvpp, tvpa and tvps) and their platinum(II) (48) and rhodium(I) (49) complexes. 

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