The reactivity of tBuLi towards aromatic –PCH–N-heterocycles is solvent-controlled.

Selective CH-lithiation at –PCH–NMe– species is achieved in THF or Et₂O/KOtBu.

In hexane sterically congested tBuP-C(SiMe₃)₂-NMe ligands are formed with excess tBuLi/ClSiMe₃.

In toluene tBuLi/ClSiMe₃ react with –PCH–NMe– preferably to –Me₃SiP-CHtBu-NMe species.

tBuLi/ClSiMe₃ and –PCH–NH– give preferably –tBuP-CH(SiMe₃)-N(SiMe₃) species.