Abstract19F and31P decoupling experiments are used to simplify the proton spectra ofpara‐substituted derivatives of triphenyl phosphine, prior to1H‐{1H} tickling experiments.3J(31P…︁H) and4J(31P…︁H) are positive, and5J(31P…︁19F) is negative in the trivalent phosphorus derivatives, and all become more positive as the valency of the phosphorus atom is increased. A triple resonance experiment is used to show that7J(31P…︁H) in [p‐CH3C6H4CH2P⊕(C6H5)3] is negative. The double resonance technique is used to relate the31P chemical shifts to the tetramethylsi