[W(CO)5]-coordinated phosphine triflates undergo electrophilic substitution reactions with ferrocene. We have used this methodology to add PPh2 and PPhCl units to the 1 and 1âČ positions of ferrocene to form tungsten pentacarbonyl complexes of 1,1âČ-bisdiphenylphosphinoferrocene, 1,1âČ-bischlorophenylphosphinoferrocene, and 1-diphenylphosphino-1âČ-chlorophenylphosphinoferrocene. The chlorophenylphosphinoferrocenes can be converted to phosphine triflates, and undergo further electrophilic substitutions, allowing us to introduce additional ferrocenyl, allyl, and alkynyl groups, forming tungsten pentacarbonyl complexes of C10H8Fe(PPh2)(PPhR) and C10H8Fe(PPhR)2 (R = allyl, phenylalkynyl, ferrocenyl).