1H NMR Studies on the Interactions of Acyclic Polyethers with Dimethyltin Dichloride in Aromatic Solvents

Article abstract of DOI:10.1246/bcsj.54.2964

The interactions between various acyclic polyethers, RO(CH2CH2O)nR'(R, R'=CH3, Ph), and dimethyltin dichloride (DMTC) in aromatic solvents have been studied by means of 1H NMR spectroscopy.On the basis of a continuous variation method, the formation of the 1:1 complexes between glymes, CH3O(CH2CH2O)nCH3 (n=2, 3, 4), and DMTC was revealed in benzene.The ²J(119Sn-CH3) values suggested distorted trans-octahedral configurations for these complexes.From the statistical consideration of stability constants, it was found that the coordination occurred virtually through neighboring two oxygen atoms in these complexes.DMTC gave the complexes of both 1:1 and 1:2 glyme/DMTC stoichiometry with glymes (n=5, 6) in benzene and with all glymes employed here in toluene and 1-chloronaphthalene.Coexistence of 1:1 and 1:2 species was also encountered for PhO(CH2CH2O)nCH3 (n=3, 4, 5), whereas no appreciable interaction was observed between PhO(CH2CH2O)nPh (n=2, 3, 4) and DMTC.On the basis of these observations, the additional formation of the 1:2 complexes was assumed to be caused by the bulkiness of polyethers.