AbstractThe rate of alkylation of (2‐N,N‐dimethylaminophenyl)diphenylphosphine with benzyl bromide in chloroform is faster than that of the corresponding reaction of (4‐N,N‐dimethylaminophenyl)diphenylphosphine. This result is discussed in terms of a through‐space N2p–P(IV) interaction for the former.The rate of alkaline cleavage of benzyl(4‐N,N‐dimethylaminophenyl)diphenylphosphonium bromide, which gives toluene, is slower than the rate of alkaline cleavage of benzyl(2‐N,N‐dimethylaminophenyl)diphenylphosphonium bromide, which gives dimethylaniline. This result is also discussed in terms of the through‐space N2p–P(IV) interaction.The31P NMR spectra of a series ofortho‐dimethylamino‐substituted triarylphosphines and benzyltriarylphosphonium halides show that the phosphorus atom is more shielded than in the correspondingpara‐dimethylamino compounds, as anticipated on the basis of an N2p–P