H(OEt2)2[P(1,2-O2C6Cl4)3]: synthesis, characterization, and application as a single-component initiator for the carbocationic polymerization of olefins.

The development of novel Brønsted acids featuring the hexacoordinate phosphorus(V) anion [TRISPHAT](-) {[1](-)=[P(1,2-O2C6Cl4)3](-)} are reported. The title compound, H(OEt2)2[1], was synthesized from 1,2-(HO)2C6Cl4 (3 equiv) and PCl5 in the presence of diethyl ether. This compound was fully characterized by (1)H, (31)P and (13)C NMR spectroscopy, X-ray crystallography and elemental microanalysis. Dissolution of H(OEt2)2[1] in acetonitrile results in the slow precipitation of crystalline H(OEt2)(NCMe)[1], which was characterized by X-ray diffraction; however, in CD2Cl2 solution the [TRISPHAT](-) anion protonated and ring-opened. The weighable, solid H(OEt2)2[1] was found to be a competent initiator for the polymerization of n-butyl vinyl ether, α-methylstyrene, styrene and isoprene at a variety of temperatures and monomer-to-initiator ratios. At low temperatures, polymers with M(n) >10(5) were obtained for n-butyl vinyl ether and α-methylstyrene whereas slightly lower molecular weights were obtained with styrene and isoprene (10(4) < M(n) <10(5)). The poly(α-methylstyrene) synthesized at -78 °C is syndiotactic-rich (ca. 87% rr) whereas the polystyrene obtained at -50 °C is atactic. The polyisoprene obtained possessed all possible modes of enchainment as well as branched and/or cyclic structures that are often observed in polyisoprene.