Quantification of ultrasound-induced chain scission in PdII-phosphine coordination polymers

J.M.J. Paulusse, J.P.J. Huijbers, R.P. Sijbesma

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A kinetically inert, reversible coordination polymer (3) was obtained through complexation of dicyclohexylphosphine telechelic poly(tetrahydrofuran) with palladium(II) dichloride. This coordination polymer is unreactive towards palladium(II) dichloride bis(1-diphenylphosphino)dodecane (4), because ligand dissociation in the coordination polymer is slow. However, upon ultrasonication of solutions of 3 in toluene in the presence of 4, formation of palladium(II) heterocomplexes was observed with 31P NMR spectroscopy. Heterocomplex formation, the consumption of 4, and changes in molecular weight were used to quantify the scission process. In the presence of 60 equivalents of the alkyldiphenylphosphine stopper complex, the reduction in molecular weight was strongly enhanced; over a period of eight hours the weight-averaged molecular weight was reduced from 1.1×105 to 2.3×104 g mol-1 while 47 % of the palladium(II) complexes in the coordination polymer had been converted into heterocomplexes. These results show that the system of 3 in combination with scavenger 4 is a suitable system to study the efficiency of ultrasound-induced chain scission of coordination polymers.
Original languageEnglish
Pages (from-to)4928-4934
JournalChemistry : A European Journal
Issue number18
Publication statusPublished - 2006


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