| The phosphoranimine Cl$sb3$P = NSiMe$sb3$ has been prepared from the reaction of PCl$sb5$ and Li(N(SiMe$sb3)sb2rbrack $ with a significant improvement in the yield (60%) over literature preparations. The related and previously unknown phosphoranimine, Cl$sb2$PhP = NSiMe$sb3$ was prepared similarily. Reactions of these phosphoranimines with various main group chlorides (PCl$sb5$, PCl$sb3$, SO$sb2rm{Cl}sb2$) afforded the well characterized products ($rm{Clsb3 P(NPClsb2)sb{n} NPClsb3rbrack lbrack PClsb6rbrack }$ (n = 0, 1, 2), Cl$sb3$P = N-PCl$sb2$, and Cl$sb3$P = NSO$sb2$Cl via the facile elimination of ClSiMe$sb3$. Similar reactions with transition metal chlorides (WCl$sb6$, TiCl$sb4$, CpTiCl$sb3$, TaCl$sb5$) were then studied. These reactions yielded the products Cl$sb3$P = N-WCl$sb5$ (1), (Cl$sb3$P = N)$sb2rm{WCl}sb4$ (2), and (Cl$sb2$PhP = N)$sb2rm{WCl}sb4$ (3), respectively. In the cases of the reactions with titanium and tantalum chlorides the products were not fully characterized.;Single crystal X-ray crystallographic studies were performed on 1 and 3. Crystals of 1 are orthorhombic, space group Pcmn, with a = 8.867(4) A, b = 10.749(2) A, c = 12.180(4) A, $alpha = beta = gamma$ = 90$spcirc$, V = 1160.9(7)A$sp3$, and Z = 4. Crystals of 3 are triclinic, space group PI with a = 9.461(4)A, b = 10.099(3)A, c = 14.506(3)A, $alpha$ = 109.65(2)$spcirc$, $beta$ = 97.88(2)$spcirc$, $gamma$ = 94.86(3)$spcirc$, V = 1280.2(7)A$sp3$, and Z = 2.;The phosphoranimine Cl$sb3$P = NSiMe$sb3$ was found to act as a monomer for a room temperature synthesis of high molecular weight linear poly(dichlorophosphazene), (N = P(Cl)$sb2rbracksb{rm n}$. In a similar fashion Cl$sb2$PhP = NSiMe$sb3$ yielded poly(phenylchlorophosphazene), (N = P(Ph)(Cl)) $sb{rm n}$ which had not previously been prepared. Both of these polymers were derivatized via a macromolecular substitution procedure with sodium trifluoroethoxide which afforded the air stable high molecular weight polymers, (N = P(OCH$sb2rm{CF}sb3)sb2rbrack sb{rm n}$ and (N = P(Ph)(OCH$sb2rm{CF}sb3)rbrack sb{rm n}$ which were then fully characterized. |
