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
Cw. Allen et al., 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, INORG CHEM, 39(4), 2000, pp. 810-814
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.