Accession Number : ADA118005

Title :   Synthesis and Stereochemistry of Some (Silylamino)phosphinimines.

Descriptive Note : Technical rept.,

Corporate Author : TEXAS CHRISTIAN UNIV FORT WORTH DEPT OF CHEMISTRY

Personal Author(s) : Neilson,Robert H ; Engenito,Joseph S , Jr

PDF Url : ADA118005

Report Date : 01 Aug 1982

Pagination or Media Count : 21

Abstract : A series of P-alkyl-P-halo substituted (silylamino)phosphinimines (Me3Si)2N-P(R)X=NSiMe3 are obtained either by oxidative addition or RI (R = Et, i-Pr, T-Bu) to (Me3Si)2N-P=NSiMe3 or by treatment of (Me3Si)2N)2PMe with I2 or Br2. Reaction of the iodophosphinimines with MeLi affords the dialkyl derivatives (Me3Si)2N-P(R)Me=NSiMe3 (R = Et, i-Pr, T-Bu). Alcoholysis of the t-BuI product in the presence of Et3N yields the N-H compounds Me3SiN(H)-P(t-Bu)OR=NSiMe3 (R = Me, CH2CF3). Variable-temperature 1H NMR studies of these (silylamino)phosphinimines demonstrate that, depending on what substituents are present, they may be fluxional via (1,3)-silyl exchange, hindered rotation about the amino P-N bond, or (1,3)-proton exchange. The results are discussed in terms of the electronic and steric effects of the phosphorus substituents. (Author)

Descriptors :   *Synthesis(Chemistry), *Stereochemistry, *Polymers, *Phosphine, Alkyl radicals, Amines, Silicon compounds, Substitution reactions, Addition reactions, Oxidation, Nuclear magnetic resonance, Spectroscopy

Subject Categories : Polymer Chemistry
      Plastics
      Atomic and Molecular Physics and Spectroscopy

Distribution Statement : APPROVED FOR PUBLIC RELEASE