Preparation of P-N-H and P-P Compounds from a Silylated Amino(Methylene) phosphine,
Abstract
Secondary amines react with the silylated amino(methylene)-phosphine (Me3Si)2NP=CHSiMe3 doublebond (1) by a complex process involving Si-N bond cleavage as well as addition tot he P-C doublebond. Thus, treatment of 1 with Et2NH yields either the N-H phosphine Me3SiN(H)P(NEt2)CH2SiMe3 (2) or the unexpected P superscript V-pIII product Me3SiN-doublebond P(NEt2)(CH2Me3)-P(CH2SiMe3)N(SiMe3)2 (3), depending upon the reaction stoichiometry. In two separate experiments iwt mechanistilc implications: (a) 2 was prepared from the reaction of Et2NH with (Me3Si)2NP(NEt)CH2SiMe3 (la), the presumed intermediate in the Et2NH/1 reaction, and (2) 3 was prepared directly by addition of the N-H compound 2 to the (methylene)phosphine 1. Compound 2 is smoothly oxidized by CCl4 to the P-chlorophosphoranimine Me3SiN-P(Cl)(NEt2)CH2SiMe3 doublebond (4) or deprotonated by n-BuLi. THe ambident anion thus formed reacts with the chlorophosphines Ph2PCl and (Me3Si)2NP(Cl)CH2SiMe3 to yield the P-P products Me3SiN-doublebond P(NEt2)(CHSiMe3)-PPh2 (5) and compound 3, respectively. (Author)
Document Details
- Document Type
- Technical Report
- Publication Date
- Oct 03, 1985
- Accession Number
- ADA159829
Entities
People
- B. L. Li
- R. H. Neilson
Organizations
- Texas Christian University