Phosphines polyether-functionalized

Several papers involving the synthesis of polyether-bound phosphines have been published previously. Okano et al. prepared tertiary phosphines 7 and 8 by Grignard reactions [14], and Harris et al. synthesized high-molecular-weight phosphines 9 and 10 through the functionalization of polyethylene glycols) (PEGs)... 

In most cases the catalytically active metal complex moiety is attached to a polymer carrying tertiary phosphine units. Such phosphinated polymers can be prepared from well-known water soluble polymers such as poly(ethyleneimine), poly(acrylic acid) [90,91] or polyethers [92] (see also Chapter 2). The solubility of these catalysts is often pH-dependent [90,91,93] so they can be separated from the reaction mixture by proper manipulation of the pH. Some polymers, such as the polyethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers, have inverse temperature dependent solubility in water and retain this property after functionalization with PPh2 and subsequent complexation with rhodium(I). The effect of temperature was demonstrated in the hydrogenation of aqueous allyl alcohol, which proceeded rapidly at 0 °C but stopped completely at 40 °C at which temperature the catalyst precipitated hydrogenation resumed by cooling the solution to 0 °C [92], Such smart catalysts may have special value in regulating the rate of strongly exothermic catalytic reactions. 

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