| Abstract: | Investigations on Lithiation and Substitution of HP[Si(t-Bu)2]2PH HP[Si(t-Bu)2]2PH 1 is monolithiated by reaction with LiPH2 · DME or LiBu in toluene. The crystalline compound HP[Si(t-Bu)2]2PLi · 2 DME 2 can be isolated in DME. Reaction of 2 with Me2SiCl2 leads to HP[Si(t-Bu)2]2P? SiMe2Cl 4 , ClMe2Si? P[Si(t-Bu)2]2P? SiMe2Cl 5 , HP[Si(t-Bu)2]2P? SiMe2? P[Si(t-Bu)2] 2PH 6 . Isomerization by Li/H migration between 4 and 2 leads to the formation of 5 . Reaction of Li(t-Bu) with 1 or 2 yields LiP[Si(t-Bu)2]2PLi 3 by further lithiation. 3 could not be obtained purely, only in a mixture with 2 . These compounds favourably generate with t-BuPCl2 in hexane Cl(t-Bu)P? P[Si(t-Bu)2]2P? P(t-Bu)Cl 9 , in THF HP[Si(t-Bu)2]2P? P(t-Bu)? P[Si(t-Bu)2]2 PH 12 (main product), 9 , H(t-Bu)P? P[Si(t-Bu)2]2P? P(t-Bu)Cl 10 , H(t-Bu)P? P[Si(t-Bu)2]2P? P(t-Bu)H 11 as well as HP[Si(t-Bu)2]2P? P(t-Bu)H 13 and HP[Si(t-Bu)2]2P? P(t-Bu)2 14 . |
