The sequential treatment of Me(Ph)PN)n with n-BuLi and electophiles such as substituted chlorosilanes, aldehydes and ketones, and carbond dioxide results in new functionalized polyphosphazenes. Graft copolymers have also been prepared by using the anionic polymer intermediate to initiate anionic addition polymerization of styrene, CH2=C(Ph)H, and ring opening polymerization of hexamethylcyclotrisiloxane (Me2SiO)3. The synthesis of polyphosphazenes, (R2P=N) n, has most generally been accomplished by substitution of poly(halophosphazenes) which are prepared by ...
The chemistry of phosphorus compounds containing Si-N-P and/or Si-C-P linkages is usually quite different from that of the nonsilylated analogues. On the one hand, the steric bulk and Pi acceptor properties of silyl groups can be used to kinetically stabilize a variety of low-coordinate phosphorus systems. Alternatively, the Si-N or Si-C bonds may serve as reactive sites so that processes such as intramolecular silyl group rearrangements and condensation reactions due ...
A series of mono(disilylamino)phosphines and two related phosphines were treated with CCl4 either neat or in CH2Cl2. The reactions proceeded with elimination of CHCl3 and/or Me3SiCCl3 to form a variety of new P-chloro-N- silylphosphoranimines. The preferential course of the reaction was dependent on solvent polarity and on the electronic and steric influence of the substituents at nitrogen and phosphorus. Complete physical and spectroscopic characterization data are given for the new ...
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