Catalytic phosphiranation has been achieved, allowing preparation of trans-1-R-2-phenyl-phosphiranes (R = t-Bu: 1-t-Bu; i-Pr: 1-i-Pr) from the corresponding dibenzo-7-(R)-7-phospha-norbornadiene (RPA, A = C14H10, anthracene) and styrene in 73% and 57% isolated yields, respectively. The cocatalyst system requires tetramethylammonium fluoride (TMAF) and [Fp(THF)][BF4] (Fp = Fe(eta(5)-C5H5)(CO)(2)). In the case of the t-Bu derivative, the reaction mechanism was probed using stoichiometric reaction studies, a Hammett analysis, and a deuterium labeling experiment. Together, these suggest the intermediacy of iron-phosphido FpP(F)(t-Bu) (2), generated independently from the stoichiometric reaction of [Fp(t-BuPA)][BF4] with TMAF. Two other plausible reaction intermediates, [Fp(t-BuPA)][BF4] and [Fp(1-t-Bu)][BF4], were prepared independently and structurally characterized.