A series of poly(ethylene-co-vinyl acetate-co-carbon monoxide) terpolymer samples with varying monomer compositions were studied using a variety of one-and two-dimensional nuclear magnetic resonance (NMR) techniques at 750 MHz. Samples were characterized in deuterated 1,4-dichlocrobenzene-d 4 at high temperature (120°C) to overcome the signal loss and broadening due to T 2 relaxation. Identification of major triads formed due to the addition of the three monomers in different permutations was facilitated by the use of different 2D techniques such as gradient assisted heteronuclear single-quantum correlation (gHSQC), gradient selected heteronuclear multiple-bond correlation (gHMBC), and gradient assisted HSQC-TOCSY. Detection of unusual structures formed due to the addition of carbon monoxide to vinyl acetate or structures due to the inversion of vinyl acetate was also possible. Because of improved dispersion the study was not restricted to the triad level, but in some cases pentads could also be identified. Distinct resonances of chain ends and short-chain branches were also observed.

Phosphazene polymers are classically synthesized by the high-temperature, ring-opening polymerization (ROP) of [PCl(2)N](3) to give [PCl(2)N](n), followed by functionalization of [PCl(2)N](n) with different side groups. We investigated the interactions of [PCl(2)N](3) with Lewis acids because Lewis acids have been used to induce the high-temperature ROP of [PCl(2)N](3). The reactions of [PCl(2)N](3) with MX(3) (M = group 13, X = halides), under strict anaerobic conditions gave adducts [PCl(2)N](3)·MX(3). Adducts were characterized by X-ray crystallography and multinuclear and variable-temperature NMR studies, and mechanistic understanding of their fluxional behavior in solution was achieved. The properties of the [PCl(2)N](3)·MX(3) adducts at or near room temperature strongly suggests that such adducts are not involved directly as intermediates in the high-temperature ROP of [PCl(2)N](3).