The inductive electron-withdrawing effect of the pos. charged P atom in triarylphosphine-BH3 adducts is largely compensated by the steric congestion caused in its vicinity. Therefore, Ph3P.BH3 reacts only sluggishly even with superbasic reagents, and products derived from ortho-metalated intermediates by their trapping with electrophiles are formed only in poor yield. However, the BH3 adducts of 3-MeOC6H4PPh2 and 3-FC6H4PPh2 are readily deprotonated at the hetero-adjacent para position and converted into final products in high yields. The P-remote regioselectivity of these phosphine-BH3 zwitterions is complementary to that previously obsd. with the corresponding phosphine oxides. [on SciFinder (R)]