Synthesis and Stereochemistry of Some (Silylamino)phosphinimines.
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)
Document Details
- Document Type
- Technical Report
- Publication Date
- Aug 01, 1982
- Accession Number
- ADA118005
Entities
People
- Joseph S. Engenito Jr
- Robert H. Neilson
Organizations
- Texas Christian University