Synthesis and spectroscopy of N3P3X5OCH = CH2 (X = Cl, F, OCH3, OCH2CF3, N(CH3)(2)) and N3P3X4(OCH = CH2)(2) (X = Cl, N(CH3)(2)). Correlations of ultraviolet photoelectron spectroscopy and nuclear magnetic resonance data to electronic and geometrical structure

The syntheses of the vinyloxycyclotriphosphazene derivatives N3P3X5OCH=CH2 (X = OMe, OCH2CF3) and the N3P3(NMe2)(4)(OCH=CH2)(2) isomeric mixture along with improved preparations of N3P3X5OCH=CH2 (X = F, NMe2) are reported. Th e interactions between the vinyloxy function and the cyclophosphazene in th ese and the previously reported N3P3Cl5 (OCH=CH2) and N3P3F6-n(OCH=CH2)(n) (n = 1-4) have been examined by ultraviolet photoelectron spectroscopy (UPS ) and NMR spectroscopy. The UPS data for the chloro and fluoro derivatives show a strong electron-withdrawing effect of the phosphazene on the olefin that is mediated with decreasing halogen substitution. The H-1 and C-13 NMR data for N3P3X5OCH=CH3 (X = F, Cl, OMe, OCH2CF3, NMe2) show significant ch anges as a function of the phosphazene substituent. There is a linear corre lation between the beta-carbon chemical shift on the vinyloxy unit and the phosphorus chemical shift at the vinyloxyphosphorus centers. The chemical s hifts of the different phosphorus centers on each ring are also related in a linear fashion. These relationships may be understood in terms of the rel ative electron donor-acceptor abilities of the substituents on the phosphaz ene ring. The H-1 NMR spectra of the N3P3(NMe2)(4)(OCH=CH2)(2) isomeric mix ture allow for assignment of the relative amounts of cis and trans isomers. A model for the observed cis preference in the formation of N3P3Cl4(OCH=CH )(2) is presented.