| 20063851 |
Bergbreiter DE, Yang YC: Variable-temperature NMR studies of soluble polymer-supported phosphine-silver complexes. J Org Chem. 2010 Feb 5;75(3):873-8.
The use of polymers as supports for organometallic catalysts has received wide attention. However, catalyst reactivity is sometimes altered as a consequence of catalyst immobilization by a polymeric ligand and such altered reactivity can complicate such supported catalysts' use. The results in this study show that heptane phase selectively soluble polyisobutylene (PIB)-bound phosphine ligands have essentially identical kinetic behavior when compared to electronically similar isobutyldiphenylphosphine analogues in phosphine coordination and exchange in silver (I) halide complexes. These studies used variable-temperature (31) P NMR spectroscopy to probe the silver-phosphine exchange processes for both AgI and AgCl complexes of these polymeric and low molecular weight phosphine ligands. The results show that the dynamic behavior of the PIB- and isobutyldiphenylphosphine-AgX complexes is nearly identical based on line-shape analysis of these (31) P NMR spectra as a function of temperature. Similar studies of more polar poly (ethylene glycol) triarylphosphine-bound AgX complexes and electronically analogous low molecular weight AgX complexes have similar behavior in variable-temperature (31) P NMR spectroscopy. |
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