Bulky alkyls, amides, and aryloxides of main Group 5 elements. Part 1. Persistent phosphinyl and arsinyl radicals ·MRR′ and their chloroprecursors MRR′Cl and related compounds

Abstract

Interaction of LiR [R = CH(SiMe₃)₂ or N(SiMe₃)₂] and MCl₃ in appropriate stoicheiometry affords the following new compounds: M[CH(SiMe₃)₂]Cl₂ or M[CH(SiMe₃)₂]₂Cl (M = P, As, or Sb), M[N(SiMe₃)₂]Cl₂ or M[N-(SiMe₃)₂]₂Cl (M = As or Sb), or Bi[N(SiMe₃)₂]₃. Reaction of P(NPrⁱ₂)Cl₂ with Li[N(SiMe₃)₂]·OEt₂, Li[N(CMe₃)(SiMe₃)], Li[CH(SiMe₃)₂], MgBu^tBr, or NHPrⁱ₂ yields the corresponding new compound P(NPrⁱ₂)RCl, while Li[CH(SiMe₃)₂] with P(NMe₂)Cl₂ affords P[CH(SiMe₃)₂](NMe₂)Cl. Reduction of the appropriate phosphorus(III) or arsenic(III) monochloride in toluene by photolysis with the olefin (Et[graphic omitted]Et gives the persistent (t½= 3 days to > 1 year in PhMe at 300 K) phosphorus(II) or arsenic(II) alkyl or amide: ·M[CH(SiMe₃)₂]₂(M = P or As), ·M[N(SiMe₃)₂]₂, ·P[CH(SiMe₃)₂](NR₂)(R = Prⁱ or SiMe₃), ·P(NPrⁱ₂)[N(SiMe₃)₂], ·P[N(CMe₃)(SiMe₃)]₂, or ·P(NPrⁱ₂)[N(CMe₃)(SiMe₃)]. Electron spin resonance parameters are discussed.