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], MgButBr, 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.